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

Abstract

The present invention addresses the problem of providing: a resin composition and a photosensitive resin composition which have excellent stability over time; a cured product; a laminate; a method for producing a cured product; a method for producing a semiconductor device; and a semiconductor device. This resin composition contains at least one resin selected from the group consisting of polyimides having an ethylenically unsaturated group and polyimide precursors having an ethylenically unsaturated group and a polymerization inhibitor having an ethylenically unsaturated group.

Description

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

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

[0002] In modern times, resin materials manufactured from resin compositions containing resins are utilized in various fields. Polyimide, in particular, is used in a wide range of applications due to its excellent heat resistance and insulating properties. For example, in semiconductor devices for packaging, it is used as an insulating film, encapsulant, and protective film. Furthermore, polyimide is known to be used in the form of resin compositions containing polyimide or polyimide precursors in the aforementioned applications.

[0003] For example, Patent Document 1 describes a resin composition containing a polyimide precursor having an ethylenically unsaturated group and a polymerization inhibitor.

[0004] Japanese Patent Publication No. 2023-124872

[0005] The resin compositions described above are required to be resistant to changes in molecular weight and other properties even during storage. In other words, they are required to have excellent stability over time. In this context, when the present inventors examined the resin compositions described in the examples of Patent Document 1, it became clear that, considering the increasing demands that are likely to arise in the future, further improvement in their stability over time is desirable.

[0006] Therefore, in view of the above circumstances, the object of the present invention is to provide a resin composition and a photosensitive resin composition that have excellent temporal stability, as well as a cured product, a laminate, a method for manufacturing a cured product, a method for manufacturing a semiconductor device, and a semiconductor device.

[0007] As a result of diligent research into the above-mentioned problems, the inventors of the present invention discovered that the stability over time can be improved by using a polymerization inhibitor having an ethylenically unsaturated group, leading to the present invention. In other words, the inventors of the present invention discovered that the above-mentioned problems can be solved by the following configuration.

[0008] (1) A resin composition comprising at least one resin selected from the group consisting of polyimides having ethylenically unsaturated groups and polyimide precursors having ethylenically unsaturated groups, and a polymerization inhibitor having ethylenically unsaturated groups. (2) The resin composition according to (1), wherein the molecular weight of the polymerization inhibitor is 1000 or less. (3) The resin composition according to (1) or (2), wherein the ethylenically unsaturated group of the polymerization inhibitor is a styryl group. (4) The resin composition according to any one of (1) to (3), wherein the polymerization inhibitor has at least one group selected from the group consisting of nitro groups, nitroso groups, N-oxyl groups, and phenolic hydroxyl groups. (5) The resin composition according to (4), wherein the polymerization inhibitor has at least one group selected from the group consisting of nitro groups and nitroso groups. (6) The resin composition according to any one of (1) to (5), wherein the content of the polymerization inhibitor is 0.00001 to 10 parts by mass per 100 parts by mass of the resin. (7) The resin composition according to any one of (1) to (6) above, wherein the resin has at least one repeating unit selected from the group consisting of repeating units represented by formula (3) and repeating units represented by formula (4) above. (8) A photosensitive resin composition comprising the resin composition according to any one of (1) to (7) above and a polymerization initiator. (9) The photosensitive resin composition according to (8) above, further comprising a crosslinking agent. (10) A cured product obtained by curing the photosensitive resin composition according to (8) or (9) above. (11) A laminate comprising two or more layers made of the cured product according to (10) above, with a metal layer between any of the layers made of the cured product. (12) A method for producing a cured product, comprising a film forming step of applying the photosensitive resin composition according to (8) or (9) above onto a substrate to form a film. (13) A method for producing a cured product according to (12) above, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. (14) A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product described in (12) or (13) above. (15) A semiconductor device comprising the cured product described in (10) above.

[0009] As shown below, the present invention provides a resin composition and a photosensitive resin composition with excellent temporal stability, as well as a cured product, a laminate, a method for manufacturing a cured product, a method for manufacturing a semiconductor device, and a semiconductor device.

[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 atm), and the relative humidity is 50% RH. In this specification, preferred combinations are considered more preferred embodiments. In this specification, excellent temporal stability and resolution are also referred to as "excellent effects of the present invention."

[0011] [1] Resin Composition The resin composition of the present invention is a resin composition containing at least one resin selected from the group consisting of polyimides having ethylenically unsaturated groups and polyimide precursors having ethylenically unsaturated groups (hereinafter also referred to as the "specified resin") and a polymerization inhibitor having ethylenically unsaturated groups (hereinafter also referred to as the "specified polymerization inhibitor"). The resin composition of the present invention is a non-photosensitive resin composition that does not contain a polymerization initiator and does not fall under the category of the photosensitive resin composition of the present invention described later.

[0012] The resin composition of the present invention has such a structure, and is therefore believed to solve the problems described above. Although the reason is not clear, it is presumed that the specific polymerization inhibitor contained in the resin composition of the present invention has an ethylenically unsaturated group, which makes the captured radicals more stable.

[0013] The following describes each component contained in the resin composition of the present invention.

[0014] [Specific Resin] The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimides having ethylenically unsaturated groups and polyimide precursors having ethylenically unsaturated groups. Here, a polyimide precursor is a resin that undergoes a change in chemical structure to become a polyimide upon external stimuli, and a resin that undergoes a change in chemical structure to become a polyimide upon heat is preferred, and a resin that undergoes a ring-closing reaction upon heat to form a ring structure to become a polyimide is more preferred. Furthermore, a polyimide is a resin having repeating units containing imide groups in its molecular chain, and a resin that has repeating units containing imide ring structures in its molecular chain is preferred. Furthermore, if the polyimide is a linear resin, it is preferred that the polyimide is a resin having repeating units containing imide groups in its main chain, and a resin that has repeating units containing imide ring structures in its main chain is more preferred. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, an imide group 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, an imide ring structure refers to a ring structure that includes all of the two carbon atoms and nitrogen atoms in the above imide as ring members. The imide ring structure is preferably a five-membered ring. Polyimides may also be so-called polyamideimides, which have an amide group in the molecular chain in addition to an imide group. In this specification, an amide group 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.

[0015] [Ethylene-unsaturated groups] Ethylene-unsaturated groups in polyimides and polyimide precursors refer to groups having an ethylenically unsaturated bond (C=C). Furthermore, ethylenically unsaturated groups may be located at the ends of the main chain of polyimides and polyimide precursors, or in the side chains, but it is preferable for them to be located in the side chains for superior effects of the present invention. Examples of ethylenically unsaturated groups include vinyl groups, vinyl ether groups, allyl groups, isoallyl groups, 2-methylallyl groups, (meth)acrylamide groups, (meth)acryloyloxy groups, and styryl groups.

[0016] In the present invention, the ethylenically unsaturated group is preferably a (meth)acryloyloxy group or a styryl group, and more preferably a styryl group, for the reason that the effects of the present invention are superior. In particular, in the present invention, the polyimide preferably has a styryl group, and the polyimide precursor preferably has a (meth)acryloyloxy group, for the reason that the effects of the present invention are superior.

[0017] [Preferred Embodiments of Polyimide] In the present invention, for reasons that the effects of the present invention are superior, it is preferable that the polyimide having an ethylenically unsaturated group has repeating units represented by the following formula (3).

[0018] In formula (3) above, R independently represents an organic group having an ethylenically unsaturated group. n and m independently represent integers of 0 or more, where n + m represents an integer of 1 or more. X represents an organic group having 4 or more carbon atoms. Y represents an organic group having 4 or more carbon atoms.

[0019] -R- In formula (3) above, R independently represents an organic group having an ethylenically unsaturated group. Here, as an organic group having an ethylenically unsaturated group, for example, the group represented by the following formula (R-1) is preferred. Formula (R-1) *-L-ethylenically unsaturated group In formula (R-1) above, * represents the bonding site with X or Y in formula (3) above. Also, L is a single bond, an alkylene group having 1 to 12 carbon atoms, or an alkylene group having 1 to 10 carbon atoms -CH２ -One or more of them represent a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)- or -CO-, and Q represents a monovalent organic group. Further, examples of the ethylenically unsaturated group are those exemplified above, and the preferred embodiments are the same.

[0020] -n and m- In the above formula (3), n and m each independently represent an integer of 0 or more. However, n + m represents an integer of 1 or more. n is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0 or 1, for the reason that the effects of the present invention are more excellent. Also, the aspect where n is 0 is one of the preferred aspects of the present invention. m is preferably an integer of 1 or more, more preferably an integer of 1 to 4, and still more preferably 1 or 2, for the reason that the effects of the present invention are more excellent.

[0021] -X- In the above formula (3), X represents an organic group having 4 or more carbon atoms. Here, the organic group having 4 or more carbon atoms preferably includes a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4).

[0022] In the above formula (V-2), R Ｘ１ each independently represents a hydrogen atom, an alkyl group or a halogenated alkyl group. Further, in the above formula (V-3), R Ｘ２ and R Ｘ３ each independently represents a hydrogen atom or a substituent, and R Ｘ２ and R Ｘ３ may combine to form a ring structure.

[0023] In the above formula (V-2), R Ｘ１ are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or a trifluoromethyl group. The halogenated alkyl group means a group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable. In the above formula (V-3), R Ｘ２and R Ｘ３ is preferably a hydrogen atom independently. R Ｘ２ and R Ｘ３ When they combine to form a ring structure, R Ｘ２ and R Ｘ３ The structure formed by their combination is preferably a single bond, -O- or -CR ２ -, more preferably -O- or -CR ２ -, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and even more preferably a hydrogen atom.

[0024] When X in the above formula (3) is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the above formula (V-1), X is preferably a group represented by the following formula (V-1-1). In the following formula, * represents the bonding site with the four carbonyl groups to which X in formula (3) is bonded, and n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Also, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxy groups and hydrocarbon groups. Further, when n in the above formula (3) is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted by R in formula (3).

[0025] When X in the above formula (3) is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the above formula (V-2), X is preferably a group represented by the following formula (V-2-1) or formula (V-2-2). From the viewpoint of reducing the amine value in the resin, etc., a group represented by formula (V-2-2) is preferable. In this specification, a bond intersecting the side of the ring structure means substituting any of the hydrogen atoms in that ring structure. In the following formula, L Ｘ１ represents a single bond or -O-, and * represents the bonding site with the four carbonyl groups to which X in formula (3) is bonded. Also, R Ｘ１The definition and preferred embodiments of are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when n in formula (3) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (3).

[0026] If X in formula (3) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3) above, then X is preferably a group represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of reducing the dielectric constant, etc., it is preferably a group represented by formula (V-3-2). In the following formula, * represents the bonding sites with the four carbonyl groups to which X in formula (3) is bonded. Also, R Ｘ２ and R Ｘ３ The definition and preferred embodiments of are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when n in formula (3) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (3).

[0027] If X in formula (3) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4) above, it is preferable that X is a group represented by the following formula (V-4-1). In the following formula, * represents the bonding sites with the four carbonyl groups to which X in formula (3) is bonded, and n1 represents an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structure may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. Also, if n in formula (3) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (3).

[0028] -Y- In formula (3) above, Y represents an organic group having 4 or more carbon atoms. Here, it is preferable that the organic group having 4 or more carbon atoms includes a structure obtained by removing 2 or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4) above.

[0029] If Y in formula (3) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1) above, it is preferable that Y is a group obtained by removing m hydrogen atoms from the group represented by the following formula (V-1-2). In the following formula, * represents the bonding sites with the two nitrogen atoms to which Y in formula (3) is bonded, and n1 represents an integer from 1 to 5. m of the hydrogen atoms in the following structure are substituted by R in formula (3). m is synonymous with m in formula (3). Furthermore, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0030] In formula (3) above, if Y is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), Y is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant, it is preferable that Y is a group represented by formula (V-2-4). In the following formula, L Ｘ１ represents a single bond or -O-, and * represents the bonding site between Y and the two nitrogen atoms to which Y is bonded in formula (3). Also, R Ｘ１ The preferred embodiments are as described above. In the following structures, m hydrogen atoms are substituted with R in formula (3). m is synonymous with m in formula (3). Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0031] If Y in formula (3) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3) above, Y is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant, it is preferable that Y is a group represented by formula (V-3-3). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y in formula (3) is bonded. Also, R Ｘ２ and R Ｘ３ The preferred embodiments are as described above. In the following structures, m hydrogen atoms are substituted with R in formula (3). m is synonymous with m in formula (3). Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0032] If Y in formula (3) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4) above, then Y is preferably a group represented by the following formula (V-4-2). In the following formula, * represents the bonding sites with the two nitrogen atoms to which Y in formula (3) is bonded, and n1 represents an integer from 0 to 5. The embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. In the following structure, m hydrogen atoms are substituted by R in formula (3). m is synonymous with m in formula (3). Furthermore, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0033] Among these, it is preferable that X and Y in formula (3) each include a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4).

[0034] The reaction temperature in the reaction to obtain polyimide is preferably 120 to 350°C, and more preferably 150 to 250°C. It is also preferable to carry out the reaction at a lower temperature by adding an imidation accelerator, in which case the reaction temperature is preferably room temperature (23°C) to 160°C, and more preferably 50 to 120°C. Examples of reagents used as imidation accelerators include a combination of acetic anhydride and pyridine, or basic compounds such as γ-valerolactone, triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0035] [Preferred Embodiment of Polyimide Precursor] In the present invention, for reasons that the effects of the present invention are superior, it is preferable that the polyimide precursor having an ethylenically unsaturated group has repeating units represented by the following formula (4).

[0036] In formula (4) above, R independently represents an organic group having an ethylenically unsaturated group. n represents an integer of 0 or more. X represents an organic group having 4 or more carbon atoms. Y represents an organic group having 4 or more carbon atoms. W independently represents -O- or -NRa-. Ra represents a hydrogen atom or a monovalent organic group. Here, preferred embodiments of X, Y, R, and n in formula (4) above are the same as preferred embodiments of X, Y, R, and n in formula (3) above.

[0037] -W- In the above formula (4), W independently represents -O- or -NRa-. Ra represents a hydrogen atom or a monovalent organic group. Here, it is preferable that both Ws represent -O- or -NH-.

[0038] [Molecular Weight] In the present invention, the weight-average molecular weight (Mw) of the polyimide having ethylenically unsaturated groups is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000, for reasons that the effects of the present invention are superior. By setting the weight-average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide having ethylenically unsaturated groups, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the above multiple types of polyimide are treated as a single resin are, respectively, within the above range.

[0039] In the present invention, the weight-average molecular weight (Mw) of the polyimide precursor having ethylenically unsaturated groups is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000, for reasons that the effects of the present invention are superior. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the degree of dispersion of the molecular weight of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight. When the resin composition contains multiple polyimide precursors having ethylenically unsaturated groups, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the multiple polyimide precursors as a single resin are each within the above ranges.

[0040] [Content] In the resin composition of the present invention, the content of the specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more, based on the total solid content of the composition, for the reason that the effects of the present invention are superior. Furthermore, in the resin composition of the present invention, the content of the specific resin is preferably 99.999999% by mass or less, more preferably 99.99999% by mass or less, even more preferably 99.999% by mass or less, even more preferably 99.99% by mass or less, and even more preferably 99.9% by mass or less, based on the total solid content of the composition. The resin composition of the present invention may contain only one type of 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.

[0041] Certain resins are typically synthesized by polymerizing compounds containing acid anhydrides, hydroxyl groups, amino groups, etc. Therefore, certain resins may contain compounds containing carboxylic acids, hydroxyl groups, amino groups, etc.

[0042] [Specific Polymerization Inhibitor] The resin composition of the present invention contains a polymerization inhibitor having an ethylenically unsaturated group (specific polymerization inhibitor). Here, a polymerization inhibitor refers to a compound that has the function of delaying or inhibiting polymerization reactions.

[0043] [Ethylene-unsaturated group] The definition, specific examples, and preferred embodiments of an ethylenically unsaturated group are the same as those of the ethylenically unsaturated group of the specific resin described above.

[0044] [Preferred Embodiments] For reasons that the effects of the present invention are superior, the specific polymerization inhibitor is preferably having at least one group selected from the group consisting of a nitro group, a nitroso group, an N-oxyl group, and a phenolic hydroxyl group (hereinafter also referred to as "functional group X1"), and more preferably having at least one group selected from the group consisting of a nitro group and a nitroso group (hereinafter also referred to as "functional group X2").

[0045] The specific polymerization initiator is preferably a compound represented by the following formula (A) for the reason that the effects of the present invention are superior. Formula (A) (X) ｎ -R- (L-ethylenically unsaturated group) ｍ In formula (A), X represents a group having the functional group X1 described above, R represents a single bond or an n+m valence organic group, and L represents a single bond or a divalent linking group. n and m each independently represent an integer of 1 or more. However, if R is a single bond, n and m are 1.

[0046] The functional group X1 is preferably the functional group X2 described above for the reason that the effects of the present invention are superior. Furthermore, X is preferably a ring structure having the functional group X2 as a substituent for the reason that the effects of the present invention are superior. Examples of the above ring structure include alicyclic rings having 3 to 12 carbon atoms and aromatic rings having 6 to 20 carbon atoms. The above ring structure is preferably an aromatic ring for the reason that the effects of the present invention are superior. Specific examples of alicyclic rings having 3 to 12 carbon atoms include cycloalkane rings such as cyclohexane rings, cyclopeptane rings, cyclooctane rings, cyclododecane rings, and cyclodocosane rings. Examples of aromatic rings having 6 to 20 carbon atoms include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthroline rings; and aromatic heterocyclic rings such as furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings.

[0047] Examples of divalent linking groups represented by R include, for example, divalent aliphatic hydrocarbon groups (especially alkylene groups), divalent aromatic hydrocarbon groups (especially arylene groups), -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-O-, -S-, -S(=O)-, and -SO ２ Examples include -, -NR- (R: hydrogen atom or substituent (for example, specific examples described later)), and groups combining these.

[0048] The specific examples of the divalent linking group represented by L are the same as those for R mentioned above.

[0049] n and m are more preferably integers from 1 to 5, more preferably integers from 1 to 3, and even more preferably 1, respectively, for reasons that the effects of the present invention are superior.

[0050] The definition, specific examples, and preferred embodiments of an ethylenically unsaturated group are the same as those of the ethylenically unsaturated group of the specific resin described above.

[0051] [Molecular Weight] The molecular weight of the specific polymerization inhibitor is not particularly limited, but for reasons that the effects of the present invention are superior, it is preferably 100 to 2000, more preferably 150 to 1000, and even more preferably 200 to 400.

[0052] [Content] In the resin composition of the present invention, the content of the specific polymerization inhibitor is preferably 0.000001 to 20 parts by mass, more preferably 0.00001 to 10 parts by mass, even more preferably 0.0001 to 5 parts by mass, even more preferably 0.001 to 3 parts by mass, and particularly preferably 0.01 to 1 part by mass, per 100 parts by mass of the specified resin, for reasons that the effects of the present invention are superior.

[0053] [2] Photosensitive resin composition The photosensitive resin composition of the present invention (hereinafter also referred to as "the photosensitive composition of the present invention") is a photosensitive resin composition containing the resin composition of the present invention described above and a polymerization initiator.

[0054] The photosensitive composition of the present invention, like the resin composition of the present invention, exhibits excellent temporal stability due to the presence of a specific polymerization inhibitor. In addition to temporal stability, the photosensitive composition of the present invention also exhibits excellent resolution. The reason for this is not clear, but it is presumed to be as follows. As described above, the specific polymerization inhibitor contained in the photosensitive composition of the present invention is a polymerization inhibitor having an ethylenically unsaturated group. The specific polymerization inhibitor functions as a crosslinking agent in the exposure area (high exposure area) and as a polymerization inhibitor in the non-exposure area (low exposure area). As a result, it is thought that the image formation becomes more rectangular and the resolution is improved. Here, it is thought that the resolution is improved when a specific polymerization inhibitor having both functions in the molecule is incorporated, compared to when the polymerization inhibitor and crosslinking agent are incorporated separately. The reason for this is thought to be that in the exposure region (high exposure region), the polymerization-inhibiting structure that captures radicals in the specific polymerization inhibitor reacts with the ethylenically unsaturated group (this is likely to occur because it is intramolecular), and the polymerization reaction of the ethylenically unsaturated group proceeds more easily. In the non-exposure region (low exposure region), even if the ethylenically unsaturated group of the specific polymerization inhibitor reacts, the polymerization-inhibiting structure within the molecule inhibits it (it inhibits it efficiently because it is intramolecular).

[0055] The following describes each component contained in the photosensitive composition of the present invention.

[0056] [Specific Resin] As the photosensitive composition of the present invention contains the resin composition of the present invention as described above, it contains the specific resin described above. The specific resin is as described above.

[0057] [Content] In the photosensitive composition of the present invention, the content of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the total solid content of the composition, for the reason that the effects of the present invention are superior. Furthermore, in the photosensitive composition of the present invention, the content of the specific resin is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, based on the total solid content of the composition, for the reason that the effects of the present invention are superior.

[0058] [Specific Polymerization Inhibitor] As the photosensitive composition of the present invention contains the resin composition of the present invention as described above, it contains the specific polymerization inhibitor described above. The specific polymerization inhibitor is as described above.

[0059] [Content] In the photosensitive composition of the present invention, the content of the specific polymerization inhibitor is preferably 0.00001 to 30 parts by mass, more preferably 0.0001 to 15 parts by mass, even more preferably 0.001 to 10 parts by mass, even more preferably 0.01 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass, per 100 parts by mass of the specified resin, for reasons that the effects of the present invention are superior.

[0060] [Polymerization Initiator] The polymerization initiator contained in the photosensitive resin composition of the present invention may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator for the reasons that the effects of the present invention are superior. The photopolymerization initiator is preferably a photoradical polymerization initiator for the reasons that the effects of the present invention are superior. 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.

[0061] 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 －１ It 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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 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.

[0071]

[0072] 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. Additionally, oxime compounds with the following structures can also be used.

[0073] As photo-radical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169 to 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 can be used. In addition, oxime compounds having a nitro group as described in paragraphs 0208 to 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 can also be used. These contents are incorporated herein by reference. Furthermore, as photo-polymerization initiators, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used. This description is incorporated herein by reference.

[0074] [Content] In the photosensitive composition of the present invention, the content of polymerization initiators (especially photopolymerization initiators) 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 composition, for reasons that the effects of the present invention are superior. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. Note that 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.

[0075] [Crosslinking agent] The photosensitive resin composition of the present invention preferably further contains a crosslinking agent for the reason that the effects of the present invention are superior. Examples of crosslinking agents include radical crosslinking agents or other crosslinking agents.

[0076] [Radical Crosslinking Agent] The photosensitive resin composition of the present invention preferably contains a radical crosslinking agent for the reason that the effects of the present invention are superior. The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. 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.

[0077] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds, for the sake of superior effects of the present invention. 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 ethylenically unsaturated bonds 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.

[0078] 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.

[0079] 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 with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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).

[0084] 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.

[0085] 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.

[0086] 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 polymerizability. The above acid value is measured in accordance with the description in JIS K 0070:1992. As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is 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.

[0087] 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, 1,6- Hexanediol 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-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 molecular weight of the polyethylene glycol chain is about 200.

[0088] From the viewpoint of suppressing warping of the pattern (cured product), the photosensitive resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred 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, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0089] <Content> When 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 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.

[0090] 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.

[0091] [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 by photosensitization with the photoacid generator or photobase generator 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 by the action of an acid or base. The acid or base is preferably an acid or base generated from the 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.

[0092] <Content> The content of other crosslinking agents 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 particularly preferably 1.0 to 10% by mass, based on the total solid content of the composition. The composition may contain only one type of other crosslinking agent, or two or more types. If two or more types of other crosslinking agents are included, it is preferable that their total amount is within the above range.

[0093] [Base Generator] The resin composition or photosensitive resin composition of the present invention (hereinafter also simply referred to as "the 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 resin composition contains a polyimide precursor, it is preferable that the composition of the present invention contains a base generator. By containing a thermal base generator in the composition of the present invention, for example, heating can promote the cyclization reaction of the precursor, resulting in good mechanical properties and chemical resistance of the cured product, and, for example, good performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package. 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, amineimide 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.

[0094] Examples of base-generating agents include, but are not limited to, the following compounds.

[0095]

[0096] 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.

[0097] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0098] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0099] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0100] [Content] When the composition of the present invention contains a base generating agent, the content of the base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin (particularly a specific resin) in the composition, for the reason that the effects of the present invention are superior. 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.

[0101] [Solvent] The composition of the present invention preferably contains a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0102] 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, 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.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (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.).

[0103] 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.

[0104] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0105] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0106] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0107] 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.

[0108] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0109] 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.

[0110] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0111] 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, 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 combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0112] [Solvent Content] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the composition 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.

[0113] [Metal Adhesion Modifying Agent] From the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc., the composition of the present invention preferably contains a metal adhesion modifying agent. 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.

[0114] [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 products of this type of compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0115]

[0116] 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).

[0117]

[0118] 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.).

[0119] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0120] [Other Metal Adhesion Modifiers] Other metal adhesion modifiers may also be used, such as the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0121] [Content] 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 resin (especially the specific resin) in the composition. Setting the content above the lower limit will result in good adhesion between the pattern and the metal layer, and setting it below the upper limit will result in 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. When two or more types are used, it is preferable that their total is within the above range.

[0122] [Migration Inhibitor] The composition of the present invention preferably further comprises a migration inhibitor. By including a migration inhibitor, for example, when a 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.

[0123] 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.

[0124] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0125] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0126] Specific examples of migration inhibitors include the following compounds.

[0127] [Content] When the composition of the present invention contains 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 even more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition.

[0128] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0129] [Light Absorbers] The compositions 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.

[0130] [Content] The content of the light absorber relative to the total solid content of the 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.

[0131] [Surfactant] The composition of the present invention preferably contains a surfactant. Various surfactants can be used as the surfactant, 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.

[0132] By incorporating a surfactant into the composition of the present invention, the liquid properties (especially the fluidity) of the composition when it is prepared are further improved, the uniformity of the coating thickness and the liquid-saving properties can be further improved, and the ability of the composition to follow steps is increased. In other words, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. As a result, air bubbles and other particles are less likely to be included in the stepped areas, and it is possible to more favorably form a uniform film with less thickness variation.

[0133] 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.

[0134] One type of surfactant may be used, or two or more types may be used in combination.

[0135] [Content] 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.

[0136] [Other Resins] The composition of the present invention may contain other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like. For example, by further adding (meth)acrylic resin, a composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance.

[0137] [Content] If the photosensitive 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 composition, for the reason that the effects of the present invention are superior. If the photosensitive 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 composition, for the reason that the effects of the present invention are superior. In one preferred embodiment of the composition of the present invention, the content of other resins is also 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 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 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.

[0138] [Other Additives] The composition of the present invention may optionally contain various additives, such as higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregating 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 US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the composition.

[0139] [Characteristics of the composition of the present invention, etc.]

[0140] [Viscosity] The viscosity of the composition of the present invention can be adjusted by the solid content concentration of the 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.

[0141] [Moisture Content] The moisture content of the 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 composition over time is further improved. Furthermore, the lower limit of the moisture content of the 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 moisture 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 moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0142] [Metal Content] From the viewpoint of insulating properties and reliability, the metal content of the composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and 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, and adhesion, the lower limit of the metal content in the 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, and tin, but excludes metals included as complexes of organic compounds and metals. If multiple metals are included, it is preferable that the total of these metals is within the above range. Specific examples of metal content in the composition of the present invention include, for example, 0.002 ppm by mass, 0.05 ppm by mass, and 0.3 ppm by mass.

[0143] Furthermore, methods for reducing metal impurities unintentionally included in the composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the composition, performing filter filtration on the raw materials constituting the composition, and performing distillation under conditions that suppress contamination as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0144] [Content of Halogen Atoms, etc.] Considering the application of the composition of the present invention as an electronic material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of reducing wiring corrosion and device reliability. 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. Furthermore, from the viewpoint of reducing the effort required to reduce halogen ions, the lower limit of halogen ions in the composition of the present invention can be 0.01 ppm by mass or more, and can also be 0.1 ppm by mass or more. Specific examples of halogen ion amounts in the composition of the present invention include, for example, 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 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 range. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0145] [Preparation of the Composition of the Present Invention] The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Examples of 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.

[0146] For the purpose of removing foreign matter such as dirt and fine particles from the composition of the present invention, filtration using a filter is preferable. As for the filter, the contents of paragraph

[0287] of International Publication No. 2023 / 190064 can be referenced, and these contents are incorporated herein.

[0147] Conventional containers can be used as containers for the composition of the present invention. To suppress the incorporation of impurities into the raw materials and composition, 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.

[0148] [3] Cured product The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

[0149] [4] Method for Manufacturing a Cured Product The method for manufacturing a cured product of the present invention preferably includes a film-forming step of applying the photosensitive resin composition of the present invention onto a substrate to form a film. The method for manufacturing a cured product 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 a cured product 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 a cured product may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0150] [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.

[0151] [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.

[0152] When a 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.

[0153] Coating is a preferred method for applying (applying) the photosensitive resin composition to 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 application conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the application 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 the substrate is coated with various solvents to improve the wettability of the substrate before applying the photosensitive resin composition to the substrate, and then the photosensitive resin composition is applied.

[0154] [Transfer Film] A method can also be applied in which the photosensitive resin composition of the present invention is applied to a temporary support by the above application method to form a transfer film having a composition layer containing the photosensitive resin composition of the present invention on the temporary support, and the composition layer is transferred to a substrate. That is, the transfer film of the present invention is a transfer film having a temporary support and a composition layer containing the photosensitive resin composition of the present invention. Furthermore, the transfer film of the present invention may further include a cover film. Furthermore, the transfer film of the present invention may include layers other than the temporary support, the composition layer and the cover film. Examples of layers other than the temporary support, the composition layer and the cover film include a water-soluble resin layer containing a water-soluble resin such as PVA and / or PVP, a thermoplastic resin layer containing a thermoplastic resin, and an adhesion layer for providing adhesion.

[0155] - Temporary Support - The transfer film includes a temporary support. The temporary support is a component that supports the composition layer and is ultimately removed by a peeling process.

[0156] The temporary support may have either a single-layer or multi-layer structure. A film is preferred for the temporary support, and a resin film is more preferred. A film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat, is also preferred as the temporary support. Examples of the above films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, polycycloolefin film, and polycarbonate film, with polyethylene terephthalate film being preferred. It is also preferable that the temporary support does not have deformations such as wrinkles or scratches.

[0157] -Composition Layer- The composition layer is a layer containing the photosensitive resin composition of the present invention as described above. The various components that may be included in the composition layer are, for example, the same as the various components that may be included in the photosensitive resin composition of the present invention, and the preferred embodiments are the same except in terms of the solvent content. From the viewpoint of embedding properties, film handling properties, etc., the solvent content in the composition layer is preferably 0.0001% to 10% by mass, more preferably 0.0005% to 8% by mass, even more preferably 0.001% to 5% by mass, and particularly preferably 0.01% to 4% by mass, relative to the entire composition layer. The composition layer may consist of multiple layers with different components.

[0158] -Thickness- The average thickness of the composition layer is preferably 0.5 μm to 40 μm, more preferably 0.5 μm to 25 μm, and even more preferably 3 μm to 20 μm. An average thickness of 40 μm or less of the composition layer is preferable in that it provides excellent pattern resolution, and an average thickness of 0.5 μm or more of the composition layer is preferable in that it provides excellent embeddability and device reliability.

[0159] The transfer can be carried out using a known laminator. Roll type, diaphragm type, press type, vacuum pressure type, etc., can be used. Examples of commercially available laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch type vacuum pressure laminators. Regarding the transfer method, the manufacturing methods described in paragraphs 0108 to 0111 of Japanese Patent Application Publication No. 2022-39763, paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696, and paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used.

[0160] [Drying Step] After the film formation step (layer formation step), the film may be subjected to a drying step 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 step to dry the film formed in the film formation step. The drying step is preferably performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step 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.

[0161] [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.

[0162] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0163] 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.

[0164] [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.

[0165] [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.

[0166] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0167] 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, preferably those described in paragraph

[0300] of International Publication No. 2023 / 190064, and more preferably TMAH. 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0172] 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.

[0173] [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.

[0174] 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.

[0175] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), and PGME (propylene glycol monomethyl ether). More preferred are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, with cyclohexanone and PGMEA being even more preferred.

[0176] 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.

[0177] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0178] <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 using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply using a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying using 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.

[0179] 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.

[0180] [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 precursors are cyclized 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. For the heating process, reference can be made to paragraphs

[0326] to

[0332] of International Publication No. 2023 / 190064, which are incorporated herein by reference.

[0181] [Metal layer formation step] The pattern obtained by the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer formation step 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 step in which a metal layer is formed on the pattern obtained by the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step).

[0182] 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.

[0183] 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.

[0184] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0185] [Applications] Examples of applications for the cured product manufacturing method of the present invention, or for the cured product itself, 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.

[0186] 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.

[0187] [5] 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 layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0188] 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.

[0189] 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 resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0190] [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.

[0191] If a further lamination process is performed after the lamination process, a surface activation treatment process may be performed after the exposure process, the heating process, or the metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0192] 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.

[0193] In the present invention, it is particularly preferable to form a cured product (resin layer) of the 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 resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0194] [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 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 resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the 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 post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0195] [6] Semiconductor device and method for manufacturing the same. The present invention also discloses a semiconductor device comprising a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device comprising a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the 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.

[0196] 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.

[0197] [Synthesis of polymerization inhibitors]

[0198] [Synthesis of A-1] Dissolve 10.0 g (71.9 mmol) of o-nitrophenol in 145 ml of NEP (N-ethyl-2-pyrrolidone), add 11.0 g (71.9 mmol) of 4-chloromethylstyrene, 14.9 g (108 mmol) of potassium carbonate, and 1.79 g (10.8 mmol) of potassium iodide, and stir at 90°C for 1 hour. Filter the resulting solution to remove the salt, then add 300 ml of 0.1 M aqueous hydrochloric acid and 300 ml of ethyl acetate, and remove the aqueous layer after liquid-liquid separation. Wash the resulting ethyl acetate solution three times with saturated saline solution and dry over magnesium sulfate. Filter to remove magnesium sulfate, then concentrate the ethyl acetate under reduced pressure to obtain A-1.

[0199] A-1

[0200] [Synthesis of A-2 to A-4] These compounds are synthesized in the same manner as A-1, except that the compound species and quantities are adjusted as appropriate.

[0201] A-2

[0202] A-3

[0203] A-4

[0204] [Synthesis of A-5] Dissolve 10.0 g (71.9 mmol) of p-nitrophenol in 145 ml of NEP, add 21.9 g (158 mmol) of pyridine, stir, and then cool to 0°C. Next, add 7.51 g (71.9 mmol) of methacrylate chloride dropwise to this mixture over 15 minutes and stir for 1 hour. Add 300 ml of 0.1 M aqueous hydrochloric acid solution and 300 ml of ethyl acetate to the resulting solution, perform liquid-liquid extraction, and remove the aqueous layer. Wash the resulting ethyl acetate solution three times with saturated saline solution and dry over magnesium sulfate. After filtering to remove magnesium sulfate, concentrate the ethyl acetate under reduced pressure to obtain A-5.

[0205] A-5

[0206] [Synthesis of A-6] 10.0 g (57.7 mmol) of 1-nitroso-2-naphthol was dissolved in 145 ml of NEP, and 8.96 g (57.7 mmol) of 2-(acryloyl)ethyl isocyanate and 0.07 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) were added, and the mixture was stirred for 3 hours. 300 ml of 0.1 M aqueous hydrochloric acid solution and 300 ml of ethyl acetate were added to the resulting solution, and the aqueous layer was removed after liquid-liquid extraction. The resulting ethyl acetate solution was washed three times with saturated saline solution and dried over magnesium sulfate. After filtering to remove magnesium sulfate, the ethyl acetate was concentrated under reduced pressure to obtain A-6.

[0207] A-6

[0208] [Synthesis of polyimides]

[0209] [Synthesis of P-1] 26.0 g (50.0 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (BPADA), 12.0 g (46.5 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and 0.76 g (7.00 mmol) of 4-aminophenol (PAP) are dissolved in 250 ml of NEP. The mixture is stirred at 200°C for 4 hours under a nitrogen atmosphere to obtain polyimide. The resulting polyimide solution is brought to room temperature, and 3.0 g of the polymerization inhibitor (A-1) mentioned above, 19.0 g of 4-chloromethylstyrene, 20.6 g of potassium carbonate, and 2.48 g of potassium iodide are added. The mixture is stirred at 90°C for 2 hours. 500 ml of THF is added to the resulting polyimide solution, and the salts are removed by filtration. The resulting filtrate is added dropwise to 3000 ml of methanol to precipitate the polymer. The polymer, collected by filtration, is dried under reduced pressure at 40°C for one day to obtain polyimide (P-1) as a powder. The Mn and Mw of P-1 are Mn = 9,500 and Mw = 28,000. The content of the polymerization inhibitor (A-1) remaining in P-1 is shown in Table 1.

[0210] P-1 is a polyimide having repeating units represented by formula (3) above. Here, R is a group represented by formula (R-1) above (L: *1-O-CH ２ - *2 (*1: bonding site with X in formula (3), *2: bonding site with ethylenically unsaturated group in formula (R-1), ethylenically unsaturated group: styryl group), n is 0, m is 1, and X is the group represented by the above formula (V-2-2) (L Ｘ１ :-O-, R Ｘ１ : methyl group), and Y is the group represented by the above formula (V-2-3) (R Ｘ１ (This refers to a methyl group.)

[0211] [Synthesis of P-2 to P-4, P-6, P-7, P-9, P-10, P-11, P-12, and P-13] Polyimides (P-2 to P-4, P-6, P-7, P-9, P-10, P-11, P-12, and P-13) are obtained in the same manner as P-1, except that the types and amounts of acid anhydrides, diamines, amines, ethylenically unsaturated group introducers, and polymerization inhibitors are changed to those shown in Tables 1 to 3. The Mn and Mw of these polyimides are shown in Tables 1 to 3. The content of polymerization inhibitors remaining in these polyimides is also shown in Tables 1 to 3.

[0212] [Synthesis of P-14] Polyimide (P-14) is obtained in the same manner as P-12, except that the reaction conditions for the acid anhydride, diamine, and amine are changed to 150°C for 10 hours. The Mn and Mw of the polyimide are shown in Table 3. The content of polymerization inhibitors remaining in the polyimide is also shown in Table 3.

[0213] [Synthesis of P-15] Polyimide (P-15) is obtained in the same manner as P-13, except that the reaction conditions for the acid anhydride, diamine, and amine are changed to 120°C for 24 hours. The Mn and Mw of the polyimide are shown in Table 3. The content of polymerization inhibitors remaining in the polyimide is also shown in Table 3.

[0214] [Synthesis of polyimide precursors]

[0215] [Synthesis of P-5] Dissolve 16.0 g (54.4 mmol) of 4,4'-biphthalic anhydride, 14.2 g (109 mmol) of 2-hydroxyethyl methacrylate, and 3.0 g of the polymerization inhibitor (A-5) mentioned above in 80 ml of diglyceride, then add 30.1 g (218 mmol) of pyridine and stir at 60°C for 4 hours. Next, after cooling the mixture to 0°C, add 12.9 g (109 mmol) of thionyl chloride dropwise over 15 minutes and stir for 1 hour to obtain a white precipitate of pyridinium hydrochloride. Next, add 8.71 g (43.5 mmol) of 4,4'-diaminodiphenyl ether dissolved in 80 ml of NMP dropwise over 30 minutes. Stir at room temperature for 1 hour, add 15 ml of ethanol, and stir for another hour. Add the resulting solution dropwise to 2000 ml of water to precipitate the polymer. The polymer collected by filtration is dried under reduced pressure at 40°C for one day to obtain a polyimide precursor (P-5) as a powder. The Mn and Mw of the obtained P-5 are Mn = 11,000 and Mw = 28,000. The content of the polymerization inhibitor (A-5) remaining in P-5 is shown in Table 1.

[0216] P-5 is a polyimide precursor having repeating units represented by formula (4) above. Here, R is the group represented by formula (R-1) above (L: *1-C ２ H ４ -*2 (*1: bonding site with W in formula (4), *2: bonding site with ethylenically unsaturated group in formula (R-1)), ethylenically unsaturated group: methacryloyloxy group), n is 0, X is the group represented by the above formula (V-1-1) (n1: 0), Y is the group represented by the formula (V-1-2) (n1: 0), and W is -O-.

[0217] [Synthesis of P-8] Polyimide precursor (P-8) is obtained in the same manner as P-5, except that the types and amounts of acid anhydride, diamine, ethylenically unsaturated group introducer, and polymerization inhibitor are changed to those shown in Table 2. The Mn and Mw of P-8 are shown in Table 2. The content of the polymerization inhibitor (A-1) remaining in P-8 is also shown in Table 2.

[0218]

[0219]

[0220]

[0221] In Tables 1 to 3, the acid anhydrides, diamines, amines, and ethylenically unsaturated group introducing agents are as follows:

[0222] BPADA

[0223] ODPA

[0224] DSDA

[0225] BAP

[0226] ODA

[0227] PAP

[0228] 4-Chloromethylcellulose

[0229] HEMA

[0230] In Tables 1 to 3, the polymerization inhibitors A-1 to A-6 are as described above. In Tables 1 to 3, the polymerization inhibitor TEMPO is as follows.

[0231] TEMPO

[0232] [Preparation of Resin Compositions] Mix the components listed in Tables 4 to 7 to prepare each resin composition (Examples 1-1 to 1-18, Comparative Examples 1-1 to 1-2). In Tables 4 to 7, a "-" indicates that the resin composition does not contain the corresponding component. Examples 1-1 to 1-9 are resin compositions containing resin and residual specific polymerization inhibitors, similar to Synthesis Examples 1 to 9 described in Tables 1 to 2. However, in Tables 4 to 7, the content of specific polymerization inhibitors (parts by mass) per 100 parts by mass of resin is indicated (amount of specific polymerization inhibitor).

[0233] [Evaluation of the time-dependent stability of the resin composition] For the obtained resin composition, an evaluation solution adjusted with NEP to a composition concentration of 20% by mass is sealed in a sample bottle so that the void volume is 1 / 3. Then, the time-dependent stability is evaluated by the number of days until the Mw (weight-average molecular weight of polyimide or polyimide precursor) of the evaluation solution is 1.1 times or more when the sample bottle is stored at 75°C. If it is less than 48 hours, it is evaluated as C; if it is 48 hours or more but less than 120 hours, it is evaluated as B; and if it is 120 hours or more, it is evaluated as A. The results are shown in Tables 4 to 7. In practical terms, A or B is preferable, and A is more preferable.

[0234]

[0235]

[0236]

[0237]

[0238] In Tables 4-7, A-1, A-2, A-4, and A-5 of the "additional polymerization inhibitors" are as described above. In Tables 4-7, BQ of the "additional polymerization inhibitors" is as follows.

[0239] BQ

[0240] As can be seen from Tables 4 to 7, Examples 1-1 to 1-18, which contain a specific polymerization inhibitor, all exhibit excellent stability over time. Furthermore, a comparison of Examples 1-1 to 1-4 and Example 1-6 (both representing polyimide forms, with only the type of specific polymerization inhibitor differing) shows that Examples 1-1 to 1-4, in which the specific polymerization inhibitor has a styryl group, exhibit even better stability over time. Additionally, a comparison of Examples 1-5, 1-8, and 1-12 (representing polyimide precursor forms) shows that Examples 1-8 and 1-12, in which the specific polymerization inhibitor has a styryl group, exhibit even better stability over time. Furthermore, a comparison of Examples 1-1, 1-7, and 1-9 to 1-11 (comparing polyimide embodiments that differ only in the content of the specific polymerization inhibitor) shows that Examples 1-1, 1-7, and 1-10 to 1-11, in which the content of the specific polymerization inhibitor per 100 parts by mass of the specific resin is 0.0001 parts by mass or more, exhibit superior long-term stability.

[0241] On the other hand, Comparative Examples 1-1 to 1-2, which do not contain a specific polymerization inhibitor, all exhibit insufficient stability over time.

[0242] [Preparation of Photosensitive Resin Compositions] Mix the components listed in Tables 8 to 12 to prepare each photosensitive resin composition (Examples 2-1 to 2 to 20, Comparative Examples 2-1 to 2-2). In Tables 8 to 12, a "-" indicates that the photosensitive resin composition does not contain the corresponding component.

[0243] [Temporal Stability of Photosensitive Resin Composition] For the obtained photosensitive resin composition, an evaluation solution adjusted with NEP to a composition concentration of 20% by mass is sealed in a sample bottle so that the void volume is 1 / 3. Then, the temporal stability is evaluated by the number of days until the Ubbelohde viscosity of the evaluation solution is 1.5 times or more of the initial value when stored at 50°C. If it is less than 48 hours, it is evaluated as C; if it is 48 hours or more but less than 120 hours, it is evaluated as B; and if it is 120 hours or more, it is evaluated as A. The results are shown in Tables 8 to 12. In practical terms, A or B is preferable, and A is more preferable.

[0244] [Resolution] The obtained photosensitive resin composition is applied by spin coating to the surface of a copper thin layer formed on a resin substrate, and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin composition layer (film) with a film thickness of 5 μm after film formation. Subsequently, the film is exposed using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)). Exposure is performed through a mask with a hole pattern of 0.5 to 20 μm in diameter formed at 1 μm intervals, at a wavelength of 365 nm and an exposure dose of 100 mJ / cm². ２ The process is carried out as follows: The resulting exposed film is heated on a hot plate at 120°C for 1 minute. Subsequently, the film is developed with cyclopentanone as the developer for 15 seconds, rinsed with PGMEA as the rinse solution for 30 seconds, and then heated under a nitrogen atmosphere at a heating rate of 10°C / min until it reaches 230°C, at which point it is heated for 1 hour to create a hole pattern. The diameter of the smallest hole pattern is shown in the "Resolution" column of Tables 8 to 12. The smaller the diameter of the hole pattern that can be formed, the better the resolution. In practice, a diameter of 4.0 μm or less is preferable.

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] In Tables 8-12, A-1, TEMPO, and BQ are as described above.

[0251] In Tables 8 to 12, polymerization initiator C-1 and crosslinking agent D-1 are as follows:

[0252] Polymerization initiator C-1

[0253] Crosslinking agent D-1

[0254] In Tables 8 to 12, the column for "Amount of Specific Polymerization Inhibitor" represents the content (parts by mass) of the specific polymerization inhibitor per 100 parts by mass of the resin (P-1 to P-15) in the composition.

[0255] As can be seen from Tables 8 to 12, Examples 2-1 to 2-20, which contain a specific polymerization inhibitor, all exhibit excellent temporal stability and resolution. Comparing Examples 2-1 to 2-4 and Example 2-6 (polyimide configuration) (comparison of configurations differing only in the type of specific polymerization inhibitor), Examples 2-1 to 2-4, in which the specific polymerization inhibitor has a styryl group, exhibit even better temporal stability and resolution. In particular, Examples 2-1 to 2-3, in which the specific polymerization inhibitor has at least one nitro group or nitroso group, exhibit even better resolution. Comparing Examples 2-5, 2-8, and 2-12 (polyimide precursor), Examples 2-8 and 2-12, in which the specific polymerization inhibitor has a styryl group, exhibit even better temporal stability and resolution. A comparison of Examples 2-1, 2-7, 2-9 to 2-11, and 2-14 (by polyimide configuration) (comparison of configurations differing only in the content of the specific polymerization inhibitor) shows that Examples 2-1, 2-7, 2-10 to 2-11, and 2-14, in which the content of the specific polymerization inhibitor per 100 parts by mass of the specific resin is 0.0001 parts by mass or more, exhibit superior temporal stability and resolution. In particular, Examples 2-1, 2-10 to 2-11, and 2-14, in which the content of the specific polymerization inhibitor per 100 parts by mass of the specific resin is 0.03 parts by mass or more, exhibit even better resolution. Among these, Example 2-14, in which the content of the specific polymerization inhibitor is 0.07 parts by mass or more, exhibits even better resolution. A comparison between Example 2-14 and Example 2-15 (a comparison of embodiments that differ only in the type of polymerization inhibitor) shows that Example 2-14, in which the content of the specific polymerization inhibitor is 0.0001 parts by mass or more, exhibits superior resolution.

[0256] On the other hand, as can be seen from Tables 8 to 12, Comparative Examples 2-1 to 2-2, which do not contain specific polymerization inhibitors, all exhibit insufficient stability over time and resolution.

[0257] [Film formation using transfer film] In the evaluation of Examples 2-1 to 2-20, the resolution evaluation was performed in the same manner as above, except that the formation of the resin composition layer on the resin substrate on which a thin copper layer was formed on the surface was changed as follows, and it was confirmed that the same results were obtained.

[0258] [Formation of the resin composition layer] The above photosensitive resin composition is applied to a temporary support (QS62, manufactured by Toray Industries, Ltd., 16 μm thick PET (polyethylene terephthalate) film) and dried at 110°C for 3 minutes to form a resin composition layer. Furthermore, a cover film (polypropylene film, Trefan KW37, manufactured by Toray Industries, Ltd., 25 μm thick) is laminated so that it is in contact with the resin composition layer to obtain a transfer film. The thickness of the resin composition layer is set to 5 μm after drying. After peeling off the cover film from the transfer film, the resin composition layer is laminated so that it faces the surface of the copper thin layer. The lamination process involves using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700") to reduce the pressure to 13 hPa or less for 30 seconds, followed by hot pressing at 100°C and 0.74 MPa for 45 seconds, and then hot pressing again at 100°C and 0.5 MPa for 75 seconds.

Claims

1. A resin composition comprising at least one resin selected from the group consisting of polyimides having ethylenically unsaturated groups and polyimide precursors having ethylenically unsaturated groups, and a polymerization inhibitor having ethylenically unsaturated groups.

2. The resin composition according to claim 1, wherein the molecular weight of the polymerization inhibitor is 1000 or less.

3. The resin composition according to claim 1, wherein the ethylenically unsaturated group of the polymerization inhibitor is a styryl group.

4. The resin composition according to claim 1, wherein the polymerization inhibitor has at least one group selected from the group consisting of a nitro group, a nitroso group, an N-oxyl group, and a phenolic hydroxyl group.

5. The resin composition according to claim 4, wherein the polymerization inhibitor has at least one group selected from the group consisting of nitro groups and nitroso groups.

6. The resin composition according to claim 1, wherein the content of the polymerization inhibitor is 0.00001 to 10 parts by mass per 100 parts by mass of the resin.

7. The resin composition according to claim 1, wherein the resin has at least one repeating unit selected from the group consisting of repeating units represented by the following formula (3) and repeating units represented by the following formula (4). Here, in formulas (3) and (4), R independently represents an organic group having an ethylenically unsaturated group. n and m independently represent integers of 0 or more, except that n + m represents an integer of 1 or more. X represents an organic group having 4 or more carbon atoms. Y represents an organic group having 4 or more carbon atoms. W independently represents -O- or -NRa-. Ra represents a hydrogen atom or a monovalent organic group.

8. A photosensitive resin composition comprising the resin composition according to any one of claims 1 to 7 and a polymerization initiator.

9. The photosensitive resin composition according to claim 8, further comprising a crosslinking agent.

10. A cured product obtained by curing the photosensitive resin composition according to claim 8.

11. A laminate comprising two or more layers made of the cured material described in claim 10, wherein a metal layer is included between any of the layers made of the cured material.

12. A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition described in claim 8 onto a substrate to form a film.

13. A method for producing a cured product according to claim 12, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern.

14. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product as described in claim 13.

15. A semiconductor device comprising the cured product described in claim 10.

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