Photosensitive resin composition and method for producing cured product

Abstract

A photosensitive resin composition and a manufacturing method of a cured product using the photosensitive resin composition, the photosensitive resin composition containing: at least one resin selected from a polyimide and a polyamide acid ester; a compound having only one (meth)acryloyl group; and a photopolymerization initiator.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition and a method for manufacturing the cured product. Background Technology

[0002] Polyimide is used in various fields, such as insulating films for electronic devices, due to its excellent heat resistance and insulation properties.

[0003] Patent Document 1 describes a photosensitive resin composition containing a resin such as polyamic acid or polyamic ester, a photopolymerization initiator, and a polyfunctional (meth)acrylate compound.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-219850 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] When patterning a cured material is created by exposing and developing a photosensitive resin composition containing at least one resin selected from polyimide and polyimide precursors, a large focus margin is required for the photosensitive resin composition. Excellent focus margin allows for resolution regardless of the in-plane uniformity of the coating thickness, and improves the yield in semiconductor packaging manufacturing. Furthermore, patterning can be performed on substrates with stepped differences, shortening the number of steps in semiconductor packaging manufacturing.

[0009] Focus margin refers to the length of the range along the film thickness direction of the focal point of the exposure light that can form a pattern within an acceptable range when exposing a photosensitive film to form a pattern. Specifically, the focal point of the exposure light that can form the desired pattern is taken as a reference position. The focal point is moved from the reference position in the film thickness direction to find the maximum distance from the reference position that can form a pattern within the acceptable range. This distance is called the focus margin.

[0010] Multifunctional (meth)acrylate compounds have multiple (meth)acryloyl groups as polymerizable groups, resulting in high crosslinking properties and thus enabling an increase in the crosslinking density of the exposure section (cured film). However, as shown in Patent Document 1, when using only multifunctional (meth)acrylate compounds as crosslinking agents, there is a problem of low focus margin when patterning the photosensitive film.

[0011] The objective of this invention is to provide a photosensitive resin composition with excellent focusing margin and a method for manufacturing the cured product.

[0012] means for solving technical problems

[0013] The following are examples of representative embodiments of the present invention. [1]

[0015] A photosensitive resin composition comprising:

[0016] polyimide

[0017] Compound (S1) has only one (meth)acryloyl group in its molecule; and

[0018] Photopolymerization initiator. [2]

[0020] According to the photosensitive resin composition described in [1], wherein,

[0021] The above compound (S1) is 2-hydroxyethyl methacrylate. [3]

[0023] According to the photosensitive resin composition described in [1] or [2], wherein,

[0024] The above-mentioned polyimide is insoluble in alkaline aqueous solution. [4]

[0026] A photosensitive resin composition comprising:

[0027] Polyamide ester;

[0028] Compound (S2), having only one (meth)acryloyl group in its molecule and represented by the following formula (a1); and

[0029] Photopolymerization initiator.

[0030] [Chemical Formula 1]

[0031]

[0032] In formula (a1),

[0033] R 1 It represents a hydrogen atom or a methyl group.

[0034] L 1 It indicates a divalent linkage group.

[0035] X 1 Indicates -NR N1 -、-O- or -S-.

[0036] R N1 It represents a hydrogen atom or an organic group.

[0037] R 2It represents a hydrogen atom or an organic group.

[0038] R 2 With L 1 They can bond together to form a ring.

[0039] R 2 With R N1 They can bond together to form a ring. [5]

[0041] According to the photosensitive resin composition described in [4], wherein,

[0042] R in the above formula (a1) 2 It represents a hydrogen atom. [6]

[0044] According to the photosensitive resin composition described in [4], wherein,

[0045] R in the above formula (a1) 2 This indicates an organic group with a molecular weight of less than 133.0. [7]

[0047] According to the photosensitive resin composition described in [4], wherein,

[0048] The above compound (S2) is 2-hydroxyethyl methacrylate. [8]

[0050] The photosensitive resin composition according to any one of [4] to [7], wherein,

[0051] The above-mentioned polyamic acid esters are insoluble in alkaline aqueous solutions. [9]

[0053] The photosensitive resin composition according to any one of [4] to [8], wherein,

[0054] The aforementioned polyamic acid ester contains groups having olefinically unsaturated bonds.

[10]

[0056] A photosensitive resin composition comprising:

[0057] Polyamide ester;

[0058] Compound (S3), having only one (meth)acryloyl group in its molecule and represented by the following formula (a2); and

[0059] Photopolymerization initiator.

[0060] [Chemical Formula 2]

[0061]

[0062] In equation (a2),

[0063] R 3 It represents a hydrogen atom or a methyl group.

[0064] X 2 Indicates -NR N2 - or -O-.

[0065] R N2 It represents a hydrogen atom or an organic group.

[0066] R 4 It indicates an aryl group or an alkyl group having 3 or more carbon atoms.

[0067] R 4 With R N2 They can bond together to form a ring.

[11]

[0069] According to the photosensitive resin composition described in

[10] , wherein,

[0070] The above-mentioned polyamic acid esters are insoluble in alkaline aqueous solutions.

[12]

[0072] According to the photosensitive resin composition described in

[10] or

[11] , wherein,

[0073] The aforementioned polyamic acid ester contains groups having olefinically unsaturated bonds.

[13]

[0075] The photosensitive resin composition according to any one of [1] to

[12] is used to form an insulating film for a redistribution layer.

[14]

[0077] A method for manufacturing a cured material, comprising:

[0078] The film forming process involves applying the photosensitive resin composition described in any one of [1] to

[12] onto a substrate to form a film;

[0079] The exposure process selectively exposes the film formed through the above-mentioned film formation process; and

[0080] The developing process involves using a developing solution to develop the film exposed in the above-mentioned exposure process to form a pattern.

[0081] Invention Effects

[0082] According to the present invention, a method for manufacturing a photosensitive resin composition with excellent focusing margin and a cured product is provided. Detailed Implementation

[0083] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0084] In this specification, the numerical range represented by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0085] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of the process can be achieved.

[0086] In the designation of groups (atomic groups) in this specification, those without substituted and unsubstituted designations include groups (atomic groups) without substituents, and also include groups (atomic groups) with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups).

[0087] In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include bright-line spectra from mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, and activated light or radiation such as electron beams.

[0088] In this specification, "(meth)acrylate" means either "acrylate" or "methacrylate", "(meth)acrylic acid" means either "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" means either "acryloyl" or "methacryloyl".

[0089] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0090] In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0091] Unless otherwise specified in this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel permeation chromatography (GPC) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8420 GPC (manufactured by TOSOH CORPORATION) and sequentially connecting guard columns SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by TOSOH CORPORATION) in series. These molecular weights, unless otherwise specified, are obtained using NMP (N-methyl-2-pyrrolidone) as the eluent. When NMP is unsuitable as the eluent, THF (tetrahydrofuran) can also be used. Furthermore, regarding detection in GPC measurements, unless otherwise specified, a UV (ultraviolet) detector with a wavelength of 254 nm is used.

[0092] In this specification, the positional relationship of the layers constituting the laminate is referred to as "upper" or "lower" simply as long as there are other layers above or below the reference layer among the layers of interest. That is, a third layer or element may be further inserted between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Unless otherwise specified, the direction in which the layers are stacked relative to the substrate layers is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." In addition, this up-down direction is set for the convenience of explaining this specification, and in practice, the "upper" direction in this specification may also be different from vertically upward.

[0093] Unless otherwise specified in this specification, each component in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0094] Unless otherwise specified, the temperature in this instruction manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0095] In this specification, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to the bonded chain other than the main chain.

[0096] In this specification, the preferred combination of methods is a more preferred method.

[0097] [Photosensitive Resin Composition]

[0098] The photosensitive resin composition of the present invention (also referred to as "resin composition") has any one of the following first, second and third embodiments.

[0099] In the following description, "the resin composition of the present invention (also referred to as "resin composition")" may correspond to any one of the photosensitive resin compositions of the first, second and third embodiments described below.

[0100] <First Method>

[0101] The first type of photosensitive resin composition is a photosensitive resin composition (also referred to as "resin composition 1") containing polyimide, a compound having only one (meth)acryloyl group in its molecule (S1), and a photopolymerization initiator.

[0102] <Second Method>

[0103] The second type of photosensitive resin composition is a photosensitive resin composition (also referred to as "resin composition 2") containing a polyamic acid ester, a compound (S2) having only one (meth)acryloyl group in its molecule and represented by the following formula (a1), and a photopolymerization initiator.

[0104] [Chemical Formula 3]

[0105]

[0106] In formula (a1),

[0107] R 1 It represents a hydrogen atom or a methyl group.

[0108] L 1 It indicates a divalent linkage group.

[0109] X 1 Indicates -NR N1 -、-O- or -S-.

[0110] R N1 It represents a hydrogen atom or an organic group.

[0111] R 2 It represents a hydrogen atom or an organic group.

[0112] R 2 With R N1 They can bond together to form a ring.

[0113] <Third Method>

[0114] The third type of photosensitive resin composition is a photosensitive resin composition (also referred to as "resin composition 3") containing a polyamic acid ester, a compound (S3) having only one (meth)acryloyl group in its molecule and represented by the following formula (a2), and a photopolymerization initiator.

[0115] [Chemical Formula 4]

[0116]

[0117] In equation (a2),

[0118] R 3 It represents a hydrogen atom or a methyl group.

[0119] X 2 Indicates -NR N2 - or -O-.

[0120] R N2 It represents a hydrogen atom or an organic group.

[0121] R 4 It indicates an aryl group or an alkyl group having 3 or more carbon atoms.

[0122] R 4 With R N2 They can bond together to form a ring.

[0123] The mechanism by which the photosensitive resin composition of the present invention exhibits excellent focusing margin is not fully understood, but the inventors speculate as follows. However, the present invention is not limited to the following speculated mechanism.

[0124] Resin composition 1 contains polyimide and a compound (S1) as a monofunctional monomer. Compared to the polyimide precursor, the polyimide is highly polar and has low solubility in organic solvents. Therefore, as described in Patent Document 1, when used only with a highly crosslinkable polyfunctional (meth)acrylate compound as a crosslinking agent, the film will cure even at low exposure levels. Consequently, areas not intended to be cured will also cure, becoming insoluble in the developer solution, which is primarily composed of organic solvents, thus preventing the formation of the desired pattern and reducing focus margin. In contrast, in resin composition 1, by combining the polyimide with a monofunctional monomer with low crosslinkability, crosslinking at low exposure levels is appropriately suppressed. Therefore, even when exposing areas not intended to be cured at low exposure levels, curing of those areas can be suppressed, and development can be performed using a developer solution primarily composed of organic solvents. Furthermore, the areas exposed at high exposure levels (areas intended to be cured) are sufficiently cured. Therefore, it is believed that even if the focal position of the exposure light changes, the desired pattern can be formed from the low exposure zone to the high exposure zone, and the focus margin is improved.

[0125] Resin compositions 2 and 3 contain polyamic acid esters and compounds (S2) or (S3) as monofunctional monomers. Polyamic acid esters suitable for patterning processes often contain polymerizable groups on their side chains. If combined only with highly crosslinkable polyfunctional monomers as crosslinking agents, the film cannot dissolve in a developer solution primarily composed of organic solvents, even at low exposure levels. This is because polyamic acid esters have relatively high polarity; even with minimal crosslinking of side chains, the increased molecular weight significantly inhibits dissolution in organic solvents. Consequently, areas not intended to be cured will cure, becoming insoluble in the developer solution and thus failing to form the desired pattern, resulting in reduced focus margin. In contrast, in resin compositions 2 and 3, by combining polyamic acid esters with monofunctional monomers, crosslinking at low exposure levels is appropriately suppressed. Therefore, even when exposing areas not intended to be cured at low exposure levels, curing of those areas can be suppressed, and development is possible using a developer solution primarily composed of organic solvents. Furthermore, the portion exposed with high exposure (the portion intended to be cured) is fully cured. Therefore, it is believed that even if the focal point of the exposure light changes, the desired pattern can be formed from the low exposure zone to the high exposure zone, thus improving focus margin.

[0126] Furthermore, if a monofunctional (meth)acrylate compound is used in conjunction with polyamic acid instead of polyamic acid ester, the monofunctional (meth)acrylate compound has only one (meth)acryloyl group as a polymerizable group, resulting in low crosslinking properties. Additionally, since polyamic acid does not contain polymerizable groups on its side chains, the crosslinking density of the exposed portion (cured film) is significantly reduced, leading to insufficient curing. Consequently, patterning is considered difficult to perform under low exposure conditions, and the focus margin becomes smaller.

[0127] The polyimide in resin composition 1 and the polyamide esters in resin composition 2 and resin composition 3 (hereinafter collectively referred to as "specific resins") preferably contain polymerizable groups, more preferably contain free radical polymerizable groups, and even more preferably contain groups having olefinic unsaturated bonds.

[0128] In cases where a particular resin contains free radical polymerizable groups, the resin composition of the present invention preferably contains a free radical polymerization initiator. Furthermore, a sensitizer may be included as needed. Such a resin composition can, for example, form a negative photosensitive film.

[0129] Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups. When a particular resin possesses acid-decomposing groups, the resin composition preferably contains a photoacid generator. Such resin compositions can, for example, form chemically amplified positive or negative photosensitive films.

[0130] Resin composition 1, resin composition 2 and resin composition 3 can be negative photosensitive resin compositions (resin compositions capable of forming negative photosensitive films) or positive photosensitive resin compositions (resin compositions capable of forming positive photosensitive films), preferably negative photosensitive resin compositions.

[0131] [Polyimide]

[0132] The polyimide in resin composition 1 may be insoluble in alkaline aqueous solution or soluble in alkaline aqueous solution.

[0133] In this specification, "insoluble in alkaline aqueous solution" means that the mass of a 2.38% tetramethylammonium aqueous solution dissolved in 100g of the solution at 23°C is less than 0.1g.

[0134] "Soluble in alkaline aqueous solution" means that at 23°C, more than 0.1g can dissolve in 100g of a 2.38% by mass tetramethylammonium aqueous solution.

[0135] From the viewpoint of pattern formation, the polyimide in resin composition 1 can be polyimide in which 0.5g or more of a 2.38% by mass tetramethylammonium aqueous solution is dissolved in 100g of the solution at 23°C, or polyimide in which 1.0g or more of the solution is dissolved. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100g or less.

[0136] The polyimide in resin composition 1 is preferably insoluble in alkaline aqueous solution.

[0137] The polyimide in resin composition 1 is preferably soluble in a developer solution with an organic solvent as the main component.

[0138] In this specification, "developer with organic solvent as the main component" refers to a developer in which the organic solvent content is the highest among the components contained in the developer. The organic solvent content in the developer with organic solvent as the main component is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0139] Furthermore, the statement that a substance is "soluble in a developer solution with organic solvents as the main component" means that at 23°C, more than 0.1g of the substance can be dissolved in 100g of a developer solution with organic solvents as the main component.

[0140] From the viewpoint of the strength and insulation of the resulting organic film, polyimide is preferably a polyimide having multiple imide structures on the main chain.

[0141] Furthermore, the polyimide, which is the cured form of resin composition 1, is preferably insoluble in a developing solution whose main component is an organic solvent.

[0142] -Fluorine atom-

[0143] From the viewpoint of the strength of the resulting organic membrane, polyimide is also preferably provided with fluorine atoms.

[0144] Fluorine atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 More preferably, R is included as a fluorinated alkyl group in the repeating unit represented by formula (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 middle.

[0145] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0146] -Silicon atom-

[0147] From the viewpoint of the strength of the resulting organic membrane, polyimide is also preferably provided with silicon atoms.

[0148] Silicon atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 131 More preferably, the R in the repeating unit represented by formula (4) described later is included as the organic modified (poly)siloxane structure described later. 131 middle.

[0149] The aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included on the side chain of the polyimide, but preferably on the main chain of the polyimide.

[0150] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, more preferably 20% by mass or less.

[0151] -ene unsaturated bond-

[0152] From the viewpoint of the strength of the resulting organic membrane, polyimide preferably has olefinic unsaturated bonds.

[0153] Polyimide may have olefinic unsaturated bonds at the end of the main chain or in the side chain, preferably in the side chain.

[0154] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0155] The olefinic unsaturated bond is preferably contained in R in the repeating unit represented by formula (4) described later. 132 or R 131 More preferably, it is included in R as a group having an olefinic unsaturated bond. 132 or R 131 middle.

[0156] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 131 More preferably, it is included in R as a group having an olefinic unsaturated bond. 131 middle.

[0157] Examples of groups having olefinic unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups that are directly bonded to an aromatic ring and have substituted vinyl groups, (meth)acrylamido groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0158] [Chemical Formula 5]

[0159]

[0160] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0161] In equation (IV), R 21 It refers to an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkoxide group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, especially preferably 2 or 3, and the number of repetitions of the alkoxide group is preferably 1 to 12, more preferably 1 to 6, especially preferably 1 to 3) or a group formed by combining two or more of them.

[0162] As the aforementioned alkylene groups having 2 to 12 carbon atoms, they can be any of the following: linear, branched, cyclic, or a combination thereof.

[0163] As the aforementioned alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0164] Among them, R 21 Preferably, it is a group represented by any one of the following formulas (R1) to (R3), and more preferably, it is a group represented by formula (R1).

[0165] [Chemical Formula 6]

[0166]

[0167] In formulas (R1) to (R3), L represents a single bond or an alkylene group with 2 to 12 carbon atoms, a (poly)alkoxide group with 2 to 30 carbon atoms, or a group formed by bonding two or more of them; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a connection with R in formula (IV). 21 The bonding sites of the bonded oxygen atoms.

[0168] In formulas (R1) to (R3), the preferred form of L is an alkylene group having 2 to 12 carbon atoms or a (poly)alkene group having 2 to 30 carbon atoms, and is also R in formula (IV). 21 The preferred configurations are the same for alkylene groups with 2 to 12 carbon atoms or (poly)alkoxide groups with 2 to 30 carbon atoms.

[0169] In formula (R1), X is preferably an oxygen atom.

[0170] In equations (R1) to (R3), * has the same meaning as * in equation (IV), and the preferred method is also the same.

[0171] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups with a compound having isocyanate groups and olefinic unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0172] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having hydroxyl and olefinic unsaturated bonds (e.g., 2-hydroxyethyl methacrylate, etc.).

[0173] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having phenolic hydroxyl groups or other hydroxyl groups with a compound having glycidyl groups and olefinic unsaturated bonds (e.g., glycidyl methacrylate, etc.).

[0174] In formula (IV), * indicates a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

[0175] The amount of olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0176] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0177] Polyimides can contain polymeric groups other than those with olefinic unsaturated bonds.

[0178] Examples of polymerizable groups other than those with olefinic unsaturated bonds include cyclic ether groups such as epoxy and oxobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups.

[0179] Regarding polymerizable groups other than those having olefinic unsaturated bonds, for example, preferably R contained in the repeating unit represented by formula (4) described later. 131 middle.

[0180] The amount of polymerizable groups other than those having olefinic unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0181] -Polar conversion group-

[0182] Polyimide can have polar conversion groups such as acid-degradable groups.

[0183] As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. It is preferred to use acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0184] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0185] The polarity conversion base is, for example, R contained in the repeating unit represented by equation (4) described later. 131 R 132 In the end of polyimide, etc.

[0186] -Acid Value-

[0187] When polyimide is supplied to alkaline developer, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0188] The acid value is preferably below 500 mg KOH / g, more preferably below 400 mg KOH / g, and even more preferably below 200 mg KOH / g.

[0189] When polyimide is supplied for development using a developer solution with an organic solvent as the main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0190] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0191] From the viewpoint of balancing storage stability and developability, acid groups containing polyimide with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred.

[0192] pKa is a parameter used to represent the equilibrium constant Ka, expressed as its negative common logarithm, pKa, considering the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise stated, pKa is set to a value calculated based on ACD / ChemSketch (registered trademark). The value of pKa can be referenced from the values ​​described in the revised 5th edition of the *Basic Handbook of Chemistry*, compiled by the Chemical Society of Japan.

[0193] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0194] As such an acid group, the polyimide preferably contains at least one selected from carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0195] -Phenolic hydroxyl-

[0196] From the viewpoint of making the development speed appropriate based on alkaline developer, polyimide preferably has phenolic hydroxyl groups.

[0197] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0198] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by formula (4) described later. 132 or R 131 middle.

[0199] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0200] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, and preferably contains repeating units represented by the following formula (4).

[0201] [Chemical Formula 7]

[0202]

[0203] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0204] When it has polymerizable groups, the polymerizable groups can be located at R. 131 and R 132 At least one of them, as shown in formula (4-1) or formula (4-2) below, may also be located at the end of the polyimide.

[0205] Equation (4-1)

[0206] [Chemical Formula 8]

[0207]

[0208] In equation (4-1), R 133 The group is a polymerizable group, and the other groups have the same meaning as in formula (4).

[0209] Equation (4-2)

[0210] [Chemical Formula 9]

[0211]

[0212] In equation (4-2), R 134 and R 135 At least one of them is a polymeric group, and if it is not a polymeric group, it is an organic group. The other groups have the same meaning as in formula (4).

[0213] As polymerizable groups, the groups having olefinic unsaturated bonds mentioned above or polymerizable groups other than those having olefinic unsaturated bonds mentioned above can be listed.

[0214] R 131 This represents a divalent organic group. As a divalent organic group, R can be exemplified as in formula (2) described later. 111 For the same functional groups, the preferred range is also the same.

[0215] As R 131 Examples of diamine residues remaining after removing the amino group from a diamine include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) described later can be cited. 111 Examples.

[0216] From the perspective of more effectively suppressing warping during calcination, R 131 Preferably, it is a diamine residue having at least two alkylene glycol units on the main chain. More preferably, it comprises two or more diamine residues in a molecule, either an ethylene glycol chain or a propylene glycol chain, or both. Even more preferably, it is a diamine residue that does not contain an aromatic ring as the diamine.

[0217] Examples of diamines that contain two or more chains of either ethylene glycol or propylene glycol in a single molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

[0218] R 132 This represents a tetravalent organic group. Examples of tetravalent organic groups include R in formula (2) described later. 115 For the same functional groups, the preferred range is also the same.

[0219] For example, as R 115 The four bonding sites of the exemplified tetravalent organic group are bonded to the four -C (=O)- portions in formula (4) to form a condensation ring.

[0220] R 132 Examples include the tetracarboxylic acid residues remaining after the anhydride group is removed from a tetracarboxylic dianhydride. As a specific example, R in formula (2) described later can be cited. 115 Examples. From the viewpoint of the strength of organic membranes, R... 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0221] It is also preferred in R 131 and R 132 At least one of them contains an OH group. More specifically, as R 131 Preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and (DA-1) to (DA-18) described later, as R 132 As a more preferred example, (DAA-1) to (DAA-5) described later can be listed.

[0222] The polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, more preferably 20% by mass or less.

[0223] To improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0224] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are sealed with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds. Among these, monoamines are more preferably used. Preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, 1-carboxyl-5- Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0225] -Imidization rate (ring-closure rate)-

[0226] In terms of the strength and insulation properties of the obtained organic film, the imidization rate (also known as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more.

[0227] The upper limit of the imidization rate is not specifically limited, as long as it is below 100%.

[0228] The imidization rate described above can be determined, for example, by the following method.

[0229] The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure, i.e., 1377 cm⁻¹, was determined. -1 The peak intensity P1 near the target was determined. Next, the polyimide was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again, with the value at 1377 cm⁻¹ calculated. -1 The peak intensity P2 is near the target. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula.

[0230] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0231] Polyimide can contain all repeating units of R 131 and R 132 The combination of the same repeating unit represented by the above equation (4) may also include R 131 and R 132 The combination of two or more repeating units represented by the above formula (4) is different. In addition to the repeating unit represented by the above formula (4), polyimide may also contain other types of repeating units. As other types of repeating units, for example, the repeating unit represented by formula (2) described later can be listed.

[0232] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (partially replaced by a monoamine end-capping agent) at low temperature; by reacting a tetracarboxylic dianhydride (partially replaced by an anhydride, monoacyl chloride, or monoreactive ester compound end-capping agent) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (partially replaced by a monoamine end-capping agent) in the presence of a condensing agent; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid and reacting it with a diamine (partially replaced by a monoamine end-capping agent), etc., and then fully imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway to introduce a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0233] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the folding resistance of the cured film 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.

[0234] 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.

[0235] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0236] When the resin composition contains multiple polyimides, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimides are treated as a single resin are each within the above-mentioned ranges.

[0237] [Polyamic acid ester]

[0238] The polyamic acid ester in resin composition 2 and resin composition 3 may be insoluble in alkaline aqueous solution or soluble in alkaline aqueous solution.

[0239] The polyamic acid ester in resin composition 2 and resin composition 3 is preferably insoluble in alkaline aqueous solution.

[0240] The polyamic acid esters in resin composition 2 and resin composition 3 are preferably soluble in a developer solution with organic solvent as the main component.

[0241] Polyamate is a precursor of polyimide. A polyimide precursor is a resin that becomes a polyimide through a change in chemical structure caused by external stimulation, preferably a resin that becomes a polyimide through a change in chemical structure caused by heat, and more preferably a resin that becomes a polyimide through a ring-closing reaction caused by heat to form a ring structure.

[0242] Furthermore, the polyimide generated from the polyamic acid ester in resin composition 2 and resin composition 3 is preferably insoluble in a developing solution whose main component is an organic solvent.

[0243] The type of polyamide ester is not particularly limited, but it is preferred to contain repeating units represented by the following formula (2).

[0244] [Chemical Formula 10]

[0245]

[0246] In equation (2), A 1 and A 2 Each independently represents an oxygen atom or -NR. z -, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R zIt represents a hydrogen atom or a monovalent organic group. Wherein, it satisfies at least one of (i) and (ii) below.

[0247] (i)A 1 Represents an oxygen atom, and R 114 It represents a monovalent organic group.

[0248] (ii) A 2 Represents an oxygen atom, and R 113 It represents a monovalent organic group.

[0249] The repeating unit represented by equation (2) preferably satisfies both (i) and (ii) above.

[0250] A in equation (2) 1 and A 2 Each independently represents an oxygen atom or -NR. z - Preferably, oxygen atoms.

[0251] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0252] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups comprising aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the cyclic hydrocarbon groups in the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, with a preference for groups represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Their preferred ranges are as described above.

[0253] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyamic esters include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0254] Specifically, R 111Preferably, the diamine comprises a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof; more preferably, a diamine comprises an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the cyclic hydrocarbon group of the aforementioned cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0255] [Chemical Formula 11]

[0256]

[0257] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0258] In the formula, * indicates the bonding site with other structures.

[0259] As a diamine, specifically, at least one diamine selected from the following can be listed: 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine;

[0260] m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane Alkane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(2-aminophenoxy)phenyl] sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenoxy)phenyl -aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminoisocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0261] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0262] Furthermore, the diamine having two or more alkylene glycol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may preferably be used.

[0263] In terms of the flexibility of the resulting organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0264] Furthermore, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0265] [Chemical Formula 12]

[0266]

[0267] In equation (51), R 50 ~R 57 Each can be independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0268] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0269] [Chemical Formula 13]

[0270]

[0271] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0272] Examples of diamines that impart the structure of formula (51) or formula (61) include 2,2'-dimethyl-p-benzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these diamines may be used.

[0273] R in equation (2) 115 The symbol represents a tetravalent organic group. Preferably, the tetravalent organic group comprises an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents the bonding site with other structures.

[0274] [Chemical Formula 14]

[0275]

[0276] In equation (5), R 112It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0277] Regarding R 115 Specifically, examples include tetracarboxylic acid residues remaining after removing the anhydride group from tetracarboxylic dianhydrides. Polyaminates may contain only one type of tetracarboxylic acid dianhydride residue as a reactant with R. 115 The corresponding structure can also contain more than two types.

[0278] Tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0279] [Chemical Formula 15]

[0280]

[0281] In equation (O), R 115 R represents a tetravalent organic group. 115 R in equation (2) 115 They have the same meaning and the same preferred range.

[0282] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0283] Furthermore, as a preferred example, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 may also be cited.

[0284] In equation (2), R can also be used. 111 and R 115 At least one of them has an OH group. More specifically, as R 111 The residues of diaminophenol derivatives can be listed.

[0285] R in equation (2) 113 and R 114 Each can be independently represented by a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. Preferably, the polymerizable group is a free radical polymerizable group capable of cross-linking reactions through heat, free radicals, etc. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. Preferably, the free radical polymerizable group in the polyamic ester contains a group having an olefinic unsaturated bond.

[0286] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0287] [Chemical Formula 16]

[0288]

[0289] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0290] In equation (III), * indicates the bonding site with other structures.

[0291] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0292] Preferred R 201 Examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds, more preferably alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds, and even more preferably alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0293] In this invention, polyalkoxide refers to a group formed by the direct bonding of two or more alkoxide groups. The alkylene groups in the multiple alkoxide groups contained in the polyalkoxide group may be the same or different.

[0294] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0295] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and especially preferably 2.

[0296] Furthermore, the aforementioned alkylene groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0297] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0298] From the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethoxy, or groups formed by the bonding of multiple ethoxy groups and multiple propoxy groups are preferred as polyethoxy groups. Polyethoxy or polypropoxy groups are more preferred, and polyethoxy is even more preferred. Among the aforementioned groups formed by the bonding of multiple ethoxy groups and multiple propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, form blocks, or be arranged in an alternating pattern. The preferred manner for the number of repetitions of the ethoxy groups, etc., in these groups is as described above.

[0299] In equation (2), when R 113 When it is a hydrogen atom or R 114 When the hydrogen atom is present, polyamic esters can form a pair salt with tertiary amine compounds having olefinically unsaturated bonds. An example of such a tertiary amine compound with olefinically unsaturated bonds is N,N-dimethylaminopropyl methacrylate.

[0300] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal, ketal, silyl, silyl ether, tertiary alkyl ester, etc. are preferred. From the point of view of exposure sensitivity, acetal or ketal is more preferred.

[0301] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0302] The polyaminate preferably has fluorine atoms in its structure. The fluorine atom content in the polyaminate is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0303] Furthermore, to improve adhesion to the substrate, polyamic acid esters can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as diamines.

[0304] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyamic esters used in this invention is preferably a polyamic ester having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyamic ester, the range of exposure tolerance can be further expanded.

[0305] Equation (2-A)

[0306] [Chemical Formula 17]

[0307]

[0308] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0309] A 1 A 2 R 111 R 113 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 The meanings are the same, and the preferred ranges are also the same. R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0310] Polyamates may contain one repeating unit represented by formula (2), or more than two repeating units. Furthermore, they may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) described above, polyamates may also contain other types of repeating units.

[0311] As one embodiment of the polyaminate, the content of the repeating unit represented by formula (2) can be 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyaminate except for the end units can be repeating units represented by formula (2).

[0312] The weight-average molecular weight (Mw) of the polyamate is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyamate is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0313] The molecular weight dispersion of the polyamide ester is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyamide ester; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0314] In this specification, the molecular weight dispersion is a value calculated from weight-average molecular weight / number-average molecular weight.

[0315] When the resin composition contains multiple polyamic acid esters, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamic acid ester are within the above-mentioned ranges. Furthermore, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the above-mentioned multiple polyamic acid esters are treated as a single resin are each within the above-mentioned ranges.

[0316] [Manufacturing methods of polyamide esters and polyimides]

[0317] Polyamates and polyimides (hereinafter also referred to as "polyamates, etc.") can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine at low temperature; by reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamic acid, and then esterifying it using a condensing agent or an alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine in the presence of a condensing agent; by obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine, etc. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred.

[0318] Furthermore, polyimides can be synthesized using the following methods: a method for fully imidizing polyimide precursors such as polyamic acid esters or polyamic acids using known imidization reactions; a method for introducing a partial imide structure by stopping the imidization reaction midway; and a method for introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0319] Examples of condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0320] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0321] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0322] In the manufacturing methods of polyamide esters, etc., an organic solvent is preferably used during the reaction. The organic solvent can be one type or two or more types.

[0323] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0324] In the manufacturing methods of polyamide esters, etc., it is preferable to add an alkaline compound during the reaction. The alkaline compound may be one type or two or more types.

[0325] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0326] -End- Capping Agent-

[0327] In the manufacturing methods of polyaminates, etc., to further improve storage stability, it is preferable to seal the carboxylic anhydride, anhydride derivative, or amino group remaining at the resin end of the polyaminate or similar material. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin end, end-capping agents include monohydric alcohols, phenols, thiols, thiophenols, monoamines, etc., and from the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are more preferred. Preferred monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-5-aminonaphthalene. 2-Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting various end-capping agents.

[0328] Furthermore, when sealing the amino groups at the resin ends, compounds having functional groups capable of reacting with the amino groups can be used for sealing. Preferred end-capping agents for the amino groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, and benzoyl chloride.

[0329] -Solid precipitation-

[0330] Methods for manufacturing polyamide esters, etc., may include a step of precipitating a solid. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain polyamide esters, etc. To improve the purification degree, the polyamide esters, etc., can be repeatedly dissolved, reprecipitated, and dried. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0331] [Resin content]

[0332] The polyimide content in resin composition 1, relative to the total solids content of resin composition 1, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the polyimide content in resin composition 1, relative to the total solids content of resin composition 1, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0333] Resin composition 1 may contain only one type of polyimide, or it may contain two or more types. If it contains two or more types, the total amount is preferably within the above range.

[0334] The resin composition 1 preferably contains at least two resins.

[0335] Specifically, resin composition 1 may contain two or more types of polyimide and other resins (resins other than polyimide), or may contain two or more types of polyimide, preferably containing two or more types of polyimide.

[0336] Other resins include polyamic acid esters, polyamic acid, polybenzoxazole, polybenzoxazole precursors, polyamide imides, polyamide imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc.

[0337] For example, by further adding (meth)acrylic resins, resin compositions with excellent coatability can be obtained, and patterns (cured products) with excellent solvent resistance can be obtained.

[0338] For example, by using polymeric groups with a high value of polymeric groups (e.g., the molar amount of polymeric groups in 1g of resin is 1×10⁻⁶) with a weight-average molecular weight of less than 20,000. -3 Adding (more than mol / g) of (meth)acrylic resin to a resin composition can improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc.

[0339] When resin composition 1 contains other resins, the content of the other resins relative to the total solid content of resin composition 1 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.

[0340] The content of other resins in resin composition 1 relative to the total solid content of resin composition 1 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.

[0341] As a preferred embodiment of resin composition 1, it is also possible to configure the content of other resins to be low. In the above embodiment, the content of other resins relative to the total solids content of resin composition 1 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. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0342] Resin composition 1 may contain only one other resin or two or more other resins. If it contains two or more other resins, the total amount is preferably within the above range.

[0343] The content of polyamic acid ester in resin composition 2 and resin composition 3, relative to the total solid content of resin composition 2 and resin composition 3, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of polyamic acid ester in resin composition 2 and resin composition 3, relative to the total solid content of resin composition 2 and resin composition 3, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0344] Resin composition 2 and resin composition 3 may contain only one type of polyamic acid ester, or they may contain two or more types. If two or more types are contained, the total amount is preferably within the above-mentioned range.

[0345] Resin composition 2 and resin composition 3 preferably contain at least two kinds of resin.

[0346] Specifically, resin composition 2 and resin composition 3 may contain two or more polyamic esters and other resins (resins other than polyamic esters), or may contain two or more polyamic esters, preferably containing two or more polyamic esters.

[0347] When the polyamide ester contains two or more polyamide esters, it is preferable to include, for example, a structure derived from dianhydride (R as described in formula (2) above) as the polyamide ester. 115 Two or more different polyamide esters.

[0348] Other resins include polyimide, polyamic acid, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, polyamide-imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc.

[0349] For example, by further adding (meth)acrylic resins, resin compositions with excellent coatability can be obtained, and patterns (cured products) with excellent solvent resistance can be obtained.

[0350] For example, by using polymeric groups with a high value of polymeric groups (e.g., the molar amount of polymeric groups in 1g of resin is 1×10⁻⁶) with a weight-average molecular weight of less than 20,000. -3 Adding (more than mol / g) of (meth)acrylic resin to a resin composition can improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc.

[0351] When the resin composition 2 and resin composition 3 of the present invention contain other resins, the content of the other resins relative to the total solid content of the resin composition 2 and resin composition 3 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.

[0352] The content of other resins in resin composition 2 and resin composition 3 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, relative to the total solid content of resin composition 2 and resin composition 3.

[0353] As a preferred embodiment of resin composition 2 and resin composition 3, the content of other resins can also be set to a low level. In the above embodiment, the content of other resins relative to the total solid content of resin composition 2 and resin composition 3 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. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0354] Resin composition 2 and resin composition 3 may contain only one other resin or two or more other resins. If two or more other resins are contained, the total amount is preferably within the above-mentioned range.

[0355] [Compounds having only one (meth)acryloyl group in the molecule (S1)]

[0356] Resin composition 1 contains a compound (S1) having only one (meth)acryloyl group in its molecule (also referred to as "compound (S1)").

[0357] The compound (S1) is preferably a monofunctional (meth)acrylate compound or a monofunctional (meth)acrylamide compound.

[0358] The compound (S1) is more preferably the compound (S2) or compound (S3) described later, and is particularly preferably 2-hydroxyethyl methacrylate (HEMA).

[0359] Specific examples of compound (S1) include, for example, A-1 to A-16 used in the examples described later, but are not limited to these.

[0360] [A compound (S2) having only one (meth)acryloyl group in its molecule and represented by formula (a1)]

[0361] Resin composition 2 contains a compound (S2) having only one (meth)acryloyl group in the molecule and represented by the following formula (a1) (also referred to as "compound (S2)").

[0362] [Chemical Formula 18]

[0363]

[0364] In formula (a1),

[0365] R 1 It represents a hydrogen atom or a methyl group.

[0366] L 1 It indicates a divalent linkage group.

[0367] X 1 Indicates -NR N1 -、-O- or -S-.

[0368] R N1 It represents a hydrogen atom or an organic group.

[0369] R 2 It represents a hydrogen atom or an organic group.

[0370] R 2 With L 1 They can bond together to form a ring.

[0371] R 2 With R N1 They can bond together to form a ring.

[0372] R in equation (a1) 1 The preferred expression is methyl.

[0373] As in equation (a1) L 1 The divalent linking group is not particularly limited. For example, divalent organic groups can be listed, preferably alkylene, cycloalkylene, alkenylene, arylene, and groups formed by combining two or more of these groups.

[0374] The alkylene group is not particularly limited, but for example, alkylene groups with 1 to 20 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene, are preferred.

[0375] The number of carbon atoms in the cycloalkyl group is not particularly limited; for example, it is preferably 3 to 20, more preferably 4 to 15. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentylene or cyclohexylene, or a polycyclic cycloalkyl group such as norbornylene, tetracyclodecylene, tetracyclododecylene, or adamantylene. One of the methylene groups constituting the cycloalkane ring in the cycloalkyl group can be replaced by a heteroatom such as an oxygen atom, a group with a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring can be replaced by a vinylene group.

[0376] As an alkenyl group, it is not particularly limited, but for example, alkenyl groups with 2 to 8 carbon atoms are preferred.

[0377] The arylene group is not particularly limited; for example, arylene groups with 6 to 20 carbon atoms can be listed, with arylene groups having 6 to 15 carbon atoms being preferred. The arylene group is preferably phenylene or naphthylene, with phenylene being particularly preferred.

[0378] By L 1 The divalent organic group represented (e.g., the alkylene, cycloalkylene, alkenylene, and arylene groups mentioned above) may have one or more substituents. For example, an alkylene group may be replaced by a hydroxyl group.

[0379] In equation (a1), L 1 The divalent linking group is preferably a hydrocarbon group (a group consisting only of carbon and hydrogen atoms) or a group consisting only of carbon, hydrogen and oxygen atoms.

[0380] R in equation (a1) 2 It represents a hydrogen atom or an organic group.

[0381] By R 2 The organic group represented is not particularly limited, but is preferably alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, carboxyl, acyl, acyloxy, formyloxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl.

[0382] By R 2 The represented organic group may have more than one substituent. For example, an alkyl group may be substituted with a fluorine atom.

[0383] For R 2 The groups represented will be explained in more detail.

[0384] The number of carbon atoms in an alkyl group is not particularly limited; for example, it can be 1 to 20, 1 to 10, or 1 to 6. Alkyl groups can be either straight-chain or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. The same applies to the alkyl moiety in aralkyl groups, alkyl moiety in alkoxycarbonyl groups, alkyl moiety in alkylsulfonyl groups, alkyl moiety when the acyl group is an alkylcarbonyl group, and alkyl moiety when the acyloxy group is an alkylcarbonyloxy group.

[0385] Cycloalkyl groups can be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. The number of carbon atoms in a cycloalkyl group is not particularly limited; for example, it can be 5–20 or 5–15.

[0386] The alkenyl group can be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited; for example, it can be 2–20, 2–10, or 2–6.

[0387] The alkynyl group can be either straight-chain or branched. The number of carbon atoms in the alkynyl group is not particularly limited; for example, it can be 2–20, 2–10, or 2–6.

[0388] The aryl group can be either monocyclic or polycyclic (e.g., 2- to 6-rings). The number of ring-forming atoms in the aryl group is not particularly limited; for example, it can be 6-20, 6-15, or 6-10. Phenyl, naphthyl, or anthracene-yl are preferred as the aryl group, with phenyl being more preferred. The same applies to the aryl moiety in the aralkyl group, the aryl moiety in the arylsulfonyl group, the aryl moiety when the acyl group is an aryl carbonyl group, and the aryl moiety when the acyloxy group is an aryl carbonyloxy group.

[0389] The heteroaryl group can be either monocyclic or polycyclic (e.g., 2- to 6-ring). The number of heteroatoms that form the ring in the heteroaryl group is not particularly limited, and can be, for example, 1 to 10. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron. The number of ring-forming atoms in the heteroaryl group is not particularly limited, and can be, for example, 5 to 15.

[0390] When R in equation (a1) 2 When representing organic groups, it is preferable to represent organic groups with a molecular weight of 133.0 or less. An organic group with a molecular weight of 133.0 or less means that the total atomic weight of all the atoms contained in the organic group is 133.0 or less.

[0391] When R 2When representing organic groups with a molecular weight of 133.0 or less, the weakly exposed areas (regions with low exposure) are readily and appropriately dissolved in the developer solution, which is mainly composed of organic solvents, thereby improving developability. Therefore, even if the focal position of the exposure light changes, the desired pattern can be formed from the low exposure zone to the high exposure zone, and the focus margin can be improved. When R... 2 When the molecular weight of the organic group is greater than 133.0, the solubility of the developing solution of the photosensitive film increases due to the plasticizing effect, thus tending to reduce the resolution.

[0392] When R in equation (a1) 2 When representing an organic group, R 2 Preferably, it is a hydrocarbon group (a group consisting only of carbon and hydrogen atoms) or a group consisting only of carbon, hydrogen and oxygen atoms.

[0393] R in equation (a1) 2 It is especially preferred to represent hydrogen atoms.

[0394] When R 2 When representing hydrogen atoms, proton groups are introduced into the weakly exposed areas, thus allowing for easy and appropriate dissolution through interaction with carbonyl groups typically found in developers primarily composed of organic solvents, thereby improving developability. Consequently, even with variations in the focal point of the exposure light, the desired pattern can be formed from the low-exposure zone to the high-exposure zone, and focus margin can be improved.

[0395] R 2 With L 1 They can bond together to form a ring.

[0396] X in equation (a1) 1 Preferred representation -NR N1 -, -O-, or -S- represent -O-.

[0397] R N1 Indicates a hydrogen atom or an organic group.

[0398] By R N1 The description, specific examples, and preferred range of the organic groups represented are consistent with those of R in formula (a1). 2 The organic groups represented are the same.

[0399] R 2 With R N1 They can bond together to form a ring.

[0400] Compound (S2) is particularly preferred to be 2-hydroxyethyl methacrylate (HEMA).

[0401] Specific examples of compound (S2) include, for example, A-1 to A-12 used in the examples described below, but are not limited to these.

[0402] [A compound (S3) having only one (meth)acryloyl group in its molecule and represented by formula (a2)]

[0403] Resin composition 3 contains a compound (S3) having only one (meth)acryloyl group in the molecule and represented by the following formula (a2) (also referred to as "compound (S3)").

[0404] [Chemical Formula 19]

[0405]

[0406] In equation (a2),

[0407] R 3 It represents a hydrogen atom or a methyl group.

[0408] X 2 Indicates -NR N2 - or -O-.

[0409] R N2 It represents a hydrogen atom or an organic group.

[0410] R 4 It indicates an aryl group or an alkyl group having 3 or more carbon atoms.

[0411] R 4 With R N2 They can bond together to form a ring.

[0412] R in equation (a2) 3 The preferred expression is methyl.

[0413] X in equation (a2) 2 Indicates -NR N2 - or -O-.

[0414] R N2 Indicates a hydrogen atom or an organic group.

[0415] By R N2 The description, specific examples, and preferred range of the organic groups represented are consistent with those of R in formula (a1). 2 The organic groups represented are the same.

[0416] R in equation (a2) 4 It indicates an aryl group or an alkyl group having 3 or more carbon atoms.

[0417] By R 4 The aryl group can be either monocyclic or polycyclic (e.g., 2- to 6-rings). The number of cyclic atoms in the aryl group is not particularly limited; for example, it can be 6 to 20, 6 to 15, or 6 to 10.

[0418] By R 4 The aryl group may have substituents. Substituents are not particularly limited, and examples include halogen atoms (preferably fluorine, chlorine, bromine, or iodine), hydroxyl groups, amino groups, sulfonamide groups, carbamoyl groups, etc.

[0419] By R 4 The alkyl group having 3 or more carbon atoms is preferably an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 4 to 18 carbon atoms, even more preferably an alkyl group having 5 to 16 carbon atoms, and particularly preferably an alkyl group having 6 to 14 carbon atoms. The alkyl group having 3 or more carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 3 or more carbon atoms include n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2,4-dimethyl-3-pentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.

[0420] By R 4 Alkyl groups having 3 or more carbon atoms may have substituents. Substituents are not particularly limited, and examples include halogen atoms (preferably fluorine, chlorine, bromine, or iodine), hydroxyl groups, amino groups, sulfonamide groups, carbamoyl groups, etc.

[0421] R 4 Preferably, it represents an aryl group or an alkyl group having 4 or more carbon atoms; more preferably, it represents an aryl group or an alkyl group having 5 or more carbon atoms; and even more preferably, it represents an aryl group or an alkyl group having 6 or more carbon atoms.

[0422] When R 4 When substituents are present, the substituents preferably do not contain silicon atoms.

[0423] R 4 With R N2 They can bond together to form a ring.

[0424] Specific examples of compound (S3) include, for example, A-13 to A-16 used in the examples described later, but are not limited to these.

[0425] [Content of monofunctional (meth)acrylate compounds]

[0426] The content of compound (S1) in resin composition 1 is preferably 0.0020 to 20.0% by mass, more preferably 0.0040 to 15.0% by mass, and even more preferably 0.020 to 10.0% by mass, relative to resin composition 1.

[0427] The content of compound (S2) in resin composition 2 is preferably 0.0020 to 20.0% by mass, more preferably 0.0040 to 15.0% by mass, and even more preferably 0.020 to 10.0% by mass, relative to resin composition 2.

[0428] The content of compound (S3) in resin composition 3 is preferably 0.0020 to 20.0% by mass, more preferably 0.0040 to 15.0% by mass, and even more preferably 0.020 to 10.0% by mass, relative to resin composition 3.

[0429] The content (by mass) of compound (S1) contained in resin composition 1 relative to all monomer compounds (polymeric compounds) contained in resin composition 1 is preferably 0.10 to 90.0% by mass, more preferably 1.0 to 80.0% by mass, and even more preferably 2.5 to 60.0% by mass.

[0430] The content (by mass) of compound (S2) contained in resin composition 2 relative to all monomer compounds (polymeric compounds) contained in resin composition 2 is preferably 0.10 to 90.0% by mass, more preferably 1.0 to 80.0% by mass, and even more preferably 2.5 to 60.0% by mass.

[0431] The content (by mass) of compound (S3) contained in resin composition 3 relative to all monomer compounds (polymeric compounds) contained in resin composition 3 is preferably 0.10 to 90.0% by mass, more preferably 1.0 to 80.0% by mass, and even more preferably 2.5 to 60.0% by mass.

[0432] The resin composition was analyzed using liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) to identify monofunctional (meth)acrylate compounds. Furthermore, LC-MS was used to determine the standard sample and construct a calibration curve, thereby enabling the quantification of the content of monofunctional (meth)acrylate compounds in the resin composition.

[0433] <Polymerizing compounds>

[0434] The resin composition of the present invention preferably further contains a polymerizable compound that is different from the aforementioned compounds (S1), (S2) and (S3).

[0435] As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be listed.

[0436] [Free radical crosslinking agent]

[0437] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0438] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these groups contain olefinically unsaturated bonds. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0439] Preferably, (meth)acryloyl, (meth)acrylamido, or vinylphenyl are used, and (meth)acryloyl is preferred from the viewpoint of reactivity.

[0440] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may also have three or more olefinic unsaturated bonds.

[0441] As for the above-mentioned compounds having two or more olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0442] From the viewpoint of the film strength of the resulting pattern (cured product), the resin composition of the present invention preferably contains a compound having two olefinic unsaturated bonds and the above-mentioned compound having three or more olefinic unsaturated bonds.

[0443] The molecular weight of the free 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 free radical crosslinking agent is preferably 100 or more.

[0444] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds such as unsaturated phosphonic acids, styrene or other vinylbenzene derivatives, vinyl ethers, and allyl ethers can be used to replace the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0445] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at atmospheric pressure. Examples of compounds having a boiling point of 100°C or higher at atmospheric pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0446] Other preferred free radical crosslinking agents besides those mentioned above include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0447] As free radical crosslinking agents, preferred are 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 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 Co., Ltd.)) and structures formed by their (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues. They can also be used in their oligomeric form.

[0448] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups; SR-209, 231, and 239, difunctional methacrylates with four ethoxy groups (all manufactured by Sartomer Company, Inc.); DPCA-60, a hexafunctional acrylate with six pentyli groups; TPA-330, a trifunctional acrylate with three isobutyryl groups (all manufactured by Nippon Kayaku Co., Ltd.); UAS-10 and UAB-140, urethane oligomers (all manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (Nippon Kayaku Co., Ltd.). Manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0449] As free radical crosslinking agents, urethane acrylates as described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, or urethane compounds having an ethylene oxide backbone as described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418, are also preferred. Compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as free radical crosslinking agents.

[0450] The free radical crosslinking agent can also be a free radical crosslinking agent with acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent with acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent that has acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO.,LTD., such as M-510 and M-520.

[0451] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it demonstrates good polymerizability. The acid value is determined according to the description in JIS K 0070:1992.

[0452] As a free radical crosslinking agent, it is also preferred to have a free radical crosslinking agent selected from at least one of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U").

[0453] In this invention, the urea bond is formed by *-NR N -C(=O)-NR N -* indicates the key, R N Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates the bonding site with a carbon atom.

[0454] In this invention, the urethane bond is formed by *-OC(=O)-NR. N -* indicates the key, R NThe symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom, respectively.

[0455] The presence of crosslinking agent U in the resin composition can sometimes improve chemical resistance, resolution, etc.

[0456] The mechanism by which the above effects are obtained is not yet clear, but it is believed to be as follows: for example, during curing by heating or the like, a portion of the crosslinking agent U is thermally decomposed to produce amines, etc., and the amines promote the cyclization of cyclized resin precursors such as polyimide precursors.

[0457] The crosslinking agent U may have only one urea bond or urethane bond, or it may have more than one urea bond and more than one urethane bond, or it may have no urethane bond but have more than two urea bonds, or it may have no urea bond but have more than two urethane bonds.

[0458] The total number of urea bonds and urethane bonds in the crosslinking agent U is one or more, preferably one to ten, more preferably one to four, and even more preferably one or two.

[0459] When the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is one or more, preferably one to ten, more preferably one to four, and even more preferably one or two.

[0460] When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is one or more, preferably one to ten, more preferably one to four, and even more preferably one or two.

[0461] The free radical polymerizable groups in the crosslinking agent U are not particularly limited, and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0462] When the crosslinking agent U has more than two free radical polymerizable groups, the structures of each free radical polymerizable group can be the same or different.

[0463] The number of free radical polymerizable groups in the crosslinking agent U can be only 1 or more than 2, preferably 1 to 10, more preferably 1 to 6, and especially preferably 1 to 4.

[0464] The free radical polymerizable group value (mass of compound per mole of free radical polymerizable groups) in crosslinking agent U is preferably 150-400 g / mol.

[0465] From the viewpoint of the chemical resistance of the cured product, the lower limit of the free radical polymerizability group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0466] From the viewpoint of reproducibility, the upper limit of the above-mentioned free radical polymerizability group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and especially preferably 300 g / mol or less.

[0467] The polymerizability of the crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0468] The crosslinking agent U is preferably represented by the following formula (U-1).

[0469] [Chemical Formula 20]

[0470]

[0471] In equation (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR. N -, R N Z is a hydrogen atom or a monovalent organic group. U1 Z is an m-valent organic group. U2 X is an organic group with an n+1 valence, where X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0472] R U1 Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0473] R N Preferably, it is a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0474] Z U1 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or two or more of these groups bonded together, more preferably a hydrocarbon group or a hydrocarbon group bonded to a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group formed by bonding at least one of the groups in -.

[0475] As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonding. N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0476] Z U2 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or two or more of these groups bonded together, more preferably a hydrocarbon group or a hydrocarbon group bonded to a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - A group formed by bonding at least one of the groups in -.

[0477] As the aforementioned hydrocarbon group, examples of those in Z can be listed. U1 For groups that are the same as those listed, the preferred method is also the same.

[0478] X is not particularly limited and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0479] n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0480] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0481] The crosslinking agent U preferably has at least one of hydroxyl, alkoxide, amide and cyano groups.

[0482] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred.

[0483] From the viewpoint of the chemical resistance of the obtained cured film, alkene oxides with 2 to 20 carbon atoms are preferred, alkene oxides with 2 to 10 carbon atoms are more preferred, alkene oxides with 2 to 4 carbon atoms are even more preferred, ethylene or propylene oxide is even more preferred, and ethylene is particularly preferred.

[0484] The alkene oxide can be included in the crosslinking agent U as a polyalkene oxide. In this case, the number of repetitions of the alkene oxide is preferably 2 to 10, more preferably 2 to 6.

[0485] The amide group refers to the group consisting of -C(=O)-NR N - indicates the key. R N As described above, when the crosslinking agent U has an amide group, the crosslinking agent U can contain, for example, RC(=O)-NR. N -* indicates a group or is composed of *-C(=O)-NR N -R represents a group. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0486] The crosslinking agent U may have two or more structures selected from hydroxyl, alkeneoxy (wherein, when constituting polyalkeneoxy), amide and cyano groups in the molecule, but it is preferred to have only one in the molecule.

[0487] The aforementioned hydroxyl, alkeneoxy, amide, and cyano groups can be present at any position in the crosslinking agent U. However, from the viewpoint of drug resistance, the crosslinking agent U is preferably selected from at least one of the aforementioned hydroxyl, alkeneoxy, amide, and cyano groups, which is linked to at least one free radical polymerizable group contained in the crosslinking agent U through a linking group containing a urea bond or an urethane bond (hereinafter also referred to as "linking group L2-1").

[0488] In particular, when the crosslinking agent U contains only one free radical polymerizable group, it is preferable that the free radical polymerizable group contained in the crosslinking agent U is linked to at least one linking group selected from hydroxyl, alkoxy, amide and cyano groups through a linking group containing a urea bond or an urethane bond (hereinafter also referred to as "linking group L2-2").

[0489] When the crosslinking agent U contains an alkene group (wherein it is a polyalkene group when constituting a polyalkene group) and has the aforementioned linking group L2-1 or the aforementioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the alkene group (wherein it is a polyalkene group when constituting a polyalkene group) is not particularly limited, and preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. Furthermore, the preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned crosslinking agent U.

[0490] When the crosslinking agent U contains an amide group and has the aforementioned linking group L2-1 or L2-2, the structure on the side of the amide group opposite to the linking group L2-1 or L2-2 is not particularly limited, but preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. The preferred method for the free radical polymerizable group is the same as the preferred method for the free radical polymerizable group in the aforementioned crosslinking agent U. Furthermore, in the above-described manner, the carbon atom side of the amide group can be bonded to the linking group L2-1 or L2-2, and the nitrogen atom side of the amide group can also be bonded to the linking group L2-1 or L2-2.

[0491] In terms of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the crosslinking agent U preferably has hydroxyl groups.

[0492] From the viewpoint of compatibility with a particular resin, the crosslinking agent U preferably contains aromatic groups.

[0493] The aromatic groups mentioned above are preferably directly bonded to the urea or urethane bonds contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea or urethane bonds, it is preferable that one of the urea or urethane bonds is directly bonded to the aromatic group.

[0494] The aromatic group can be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a structure formed by these groups forming a condensation ring, but an aromatic hydrocarbon group is preferred.

[0495] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a group obtained by removing 2 or more hydrogen atoms from the benzene ring structure is even more preferred.

[0496] As the aforementioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further condensed with other rings, such as indole and benzimidazole.

[0497] Nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups.

[0498] The aforementioned aromatic groups are preferably included, for example, in a linking group that links two or more free radical polymerizable groups and includes a urea bond or an urethane bond, or in a linking group that links at least one of the above-mentioned hydroxyl, alkoxy, amide, and cyano groups to at least one free radical polymerizable group included in the crosslinking agent U.

[0499] The number of atoms (linking chain length) between the urea bond or urethane bond in the crosslinking agent U and the free radical polymerizable group is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.

[0500] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and contains two or more free radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bonds or urethane bonds and the free radical polymerizable groups is within the above range.

[0501] In this specification, "the number of atoms (linkage chain length) between the urea bond or urethane bond and the free radical polymerizable group" refers to the shortest (smallest number of atoms) atomic chain connecting the two atoms or groups of atoms in the path linking the linked objects. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0502] [Chemical Formula 21]

[0503]

[0504] [Axis of symmetry]

[0505] The crosslinking agent U is preferably a compound without a symmetry axis.

[0506] Crosslinking agent U lacks an axis of symmetry, meaning it does not possess an axis that allows the formation of molecules identical to the original molecule by rotating the entire compound; it is a compound that is left-right asymmetrical. Furthermore, when marking the structural formula of crosslinking agent U on paper, "crosslinking agent U lacks an axis of symmetry" means that the structural formula of crosslinking agent U cannot be marked as having an axis of symmetry.

[0507] Since the crosslinking agent U does not have a symmetry axis, it is believed that the aggregation of crosslinking agents U in the composite film can be inhibited.

[0508] [Molecular weight]

[0509] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0510] The method of manufacturing crosslinking agent U is not particularly limited; for example, it can be obtained by reacting a compound having a free radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl or an amino group.

[0511] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0512] [Chemical Formula 22]

[0513]

[0514] [Chemical Formula 23]

[0515]

[0516] [Chemical Formula 24]

[0517]

[0518] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0519] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, and 1,6-hexanediol diacrylate can be used. Acrylates, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, isocyanuric acid-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be used in combination as needed.

[0520] Additionally, for example, PEG200 diacrylate refers to a compound in which the molecular weight of the polyethylene glycol chain, which is a polyethylene glycol diacrylate, is approximately 200.

[0521] From the viewpoint of suppressing warping of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. Preferred monofunctional free radical crosslinking agents include n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl (meth)acrylamide, glycidyl methacrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and other (meth)acrylic acid derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and allyl glycidyl ether. Furthermore, to suppress volatilization before exposure, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred as monofunctional free radical crosslinking agents.

[0522] In addition, as free radical crosslinking agents with two or more functions, examples include allyl compounds such as diallyl phthalate and trimellitic acid triallyl ester.

[0523] When a free radical crosslinking agent is included, the content of the free radical crosslinking agent relative to the total solids content of the resin composition is preferably more than 0% by mass and less than 60% by mass. 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.

[0524] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used together, it is preferable that their combined dosage is within the range mentioned above.

[0525] [Other crosslinking agents]

[0526] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0527] Other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. Preferably, they are compounds that have multiple groups within their molecules that promote the formation of covalent bonds between themselves and other compounds in the composition or their reaction products by photosensitive acid or alkali generators. More preferably, they are compounds that have multiple groups within their molecules that promote the formation of covalent bonds between themselves and other compounds in the composition or their reaction products by the action of acids or bases.

[0528] The acid or base mentioned above is preferably an acid or base generated by a photoacid generator or a photoalkali generator during the exposure process.

[0529] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0530] [Photopolymerization initiator]

[0531] The resin composition of the present invention contains a photopolymerization initiator.

[0532] The preferred photopolymerization initiator is a photoradical polymerization initiator.

[0533] There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light from the ultraviolet region to the visible region are preferred. Furthermore, activators that generate active free radicals by interacting with photoexcited sensitizers can also be used.

[0534] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength range of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferable to use a UV-Vis spectrophotometer (a Cary-5 spectrophotometer manufactured by Varian) and to determine it using ethyl acetate solvent at a concentration of 0.01 g / L.

[0535] As photoradical polymerization initiators, any known compounds can be used. Examples include haloalkanes (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur 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 aromatic hydrocarbon complexes. For detailed information on these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, the following are examples of peroxide-based photopolymerization initiators described in Japanese Patent Application Publication No. 2014-130173 (paragraphs 0065 to 0111), Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol.19, No.3, 2019, international publication No. 2018 / 221177, international publication No. 2018 / 110179, Japanese Patent Application Publication No. 2019-043864, Japanese Patent Application Publication No. 2019-044030, and Japanese Patent Application Publication No. 2019-167313, which are incorporated into this specification.

[0536] Preferred oxime compounds include, for example, compounds with the following structures, or 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one, etc. Oxime compounds are preferred in resin compositions, especially as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=NOC (=O)- linking group within their molecule.

[0537] [Chemical Formula 25]

[0538]

[0539] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Co.,Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Furthermore, oxime compounds with the following structures can also be used.

[0540] [Chemical Formula 26]

[0541]

[0542] The content of photopolymerization initiator in the resin composition relative to the total solids content of the resin composition 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. It may contain only one type of photopolymerization initiator, or it may contain two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0543] [Sensitizer]

[0544] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer then comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, thereby generating free radicals, acids, or bases.

[0545] As usable sensitizers, compounds such as benzophenone, michidone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole azomethine, xanthones, phthalocyanines, benzopiperanone, and indigo compounds can be used.

[0546] Examples of sensitizers include milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzaldehyde)cyclopentane, 2,6-bis(4'-diethylaminobenzaldehyde)cyclohexanone, 2,6-bis(4'-diethylaminobenzaldehyde)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminophenylenepropyl dihydroindone. Aminobenzyl dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylethylene)benzothiazole, 2-(p-dimethylaminophenylethylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzaldehyde)acetone, 1,3-bis(4'-diethylaminobenzaldehyde)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0547] In addition, other sensitizing pigments can also be used.

[0548] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0549] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0550] [Chain transfer agent]

[0551] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Polymer Society, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0552] Furthermore, the chain transfer agent can also use compounds described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0553] When the resin composition contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. There may be only one type of chain transfer agent, or there may be two or more types. When there are two or more types of chain transfer agents, it is preferable that their total amount is within the above-mentioned range.

[0554] <Alkali generating agent>

[0555] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action.

[0556] Examples of alkali-generating agents include paragraphs 0015–0057 of International Publication No. 2015 / 199219, paragraphs 0054–0070 of International Publication No. 2018 / 025738, paragraphs 0060–0072 of International Publication No. 2019 / 189110, paragraphs 0013–0028 of International Publication No. 2019 / 189111, and paragraphs 0013–0039 of International Publication No. 2020 / 054226. Compounds described in International Publication No. 2020 / 066244, paragraphs 0101-0146; International Publication No. 2020 / 066315, paragraphs 0014-0049; International Publication No. 2020 / 066416, paragraphs 0102-0159; International Publication No. 2020 / 066435, paragraphs 0013-0050; and International Publication No. 2020 / 170997, paragraphs 0089-0100, etc. These contents are included in this specification.

[0557] When the resin composition contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of resin in the resin composition is preferably 0.1 to 50 parts by weight. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4 parts by weight or less.

[0558] One or more alkali-generating agents can be used. When using two or more, it is preferable that the total amount is within the above range.

[0559] <Solvent>

[0560] The resin composition of the present invention preferably contains a solvent.

[0561] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0562] Examples of preferred esters include, for example, 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, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid, alkyl 3-ethoxypropionic acid). Alkyl 2-alkoxypropionate esters (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-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-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0563] Examples of 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 dimethyl 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.

[0564] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro L-glucanone.

[0565] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0566] As a sulfoxide, dimethyl sulfoxide is preferably listed, for example.

[0567] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0568] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolium ketone.

[0569] 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, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0570] From the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0571] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucosidone, and dihydroL-glucosidone, or a mixture of two or more solvents. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass of toluene relative to the total mass of these solvents is also a preferred method of the invention.

[0572] In particular, from the viewpoint of the storage stability of the resin composition, the inclusion of γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and can be 100% by mass. Regarding the above content, it can be determined by considering the solubility of specific resin components or other components contained in the resin composition.

[0573] Furthermore, when using dimethyl sulfoxide and γ-valerolactone together, the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[0574] From the viewpoint of coatability, the solvent content is preferably set to a total solids concentration of 5 to 80% by mass in the resin composition of the present invention, 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 coating thickness and coating method. When two or more solvents are contained, it is preferable that their total content is within the above range.

[0575] <Metal Adhesion Modifier>

[0576] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0577] [Silane coupling agent]

[0578] As silane coupling agents, examples include compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is 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 preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0579] [Chemical Formula 27]

[0580]

[0581] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... The following are listed: 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. They can be used alone or in combination of two or more.

[0582] [Aluminum-based adhesive additives]

[0583] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate aluminum diisopropyl ester.

[0584] As other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are included in this specification.

[0585] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes good; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier may be only one type or may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0586] <Migration Inhibitor>

[0587] The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when the 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.

[0588] There are no particular limitations on the migration inhibitors, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thiourea and hydrogen sulfide groups, hindered phenolic 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 tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0589] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[0590] Other migration inhibitors, for example, include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0591] The following compounds can be cited as specific examples of migration inhibitors.

[0592] [Chemical Formula 28]

[0593]

[0594] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition 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.

[0595] There may be only one migration inhibitor or two or more. If there are two or more migration inhibitors, it is preferable that their total number falls within the above-mentioned range.

[0596] <Polymerization Inhibitor>

[0597] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0598] Specific compounds that serve as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, as well as p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radical, and phenoxazine, etc. This information is included in this specification.

[0599] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0600] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number falls within the range mentioned above.

[0601] [Organotitanium compounds]

[0602] By incorporating organotitanium compounds into the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0603] As usable organotitanium compounds, examples include compounds in which organic groups are covalently or ionicly bonded to titanium atoms.

[0604] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0605] I) Titanium chelate compounds: From the viewpoint of excellent storage stability of the resin composition and the ability to obtain good cured patterns, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(2,4-glutarate)di(n-butoxy) titanium, bis(2,4-glutarate)diisopropoxy titanium, bis(tetramethylheptyl ester)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, etc.

[0606] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0607] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0608] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzene sulfonate) isopropoxy titanium, etc.

[0609] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0610] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0611] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0612] From the viewpoint of better drug resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) diacetic titanium compound is preferred as the organotitanium compound. In particular, bis(ethyl acetoacetate)diisopropoxy titanium, tetra(n-butoxy) titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0613] When an organotitanium compound is present, its content relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the content is 0.05 parts by weight or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when the content is 10 parts by weight or less, the storage stability of the composition is better.

[0614] [Antioxidants]

[0615] By including antioxidants as additives, the elongation properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include compounds described in International Publication Nos. 2021 / 112189, 0348-0357, the contents of which are incorporated herein by reference.

[0616] The content of the antioxidant relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. By setting the addition amount to 0.1 parts by weight or more, it is easy to obtain the effect of improving elongation characteristics or adhesion to metal materials, even under high temperature and high humidity environments. Furthermore, by setting the addition amount to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0617] [Other polymers]

[0618] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyrene resins, and their copolymers. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0619] Other polymer compounds can be used alone or in combination of two or more.

[0620] When the resin composition contains other polymeric compounds, the content of the other polymeric compounds relative to the total solid content of the resin composition is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.

[0621] <Characteristics of the Resin Composition>

[0622] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components in the resin composition. From the viewpoint of coating film thickness, 1000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, further preferably 2,500mm 2 / s~8,000mm 2 / s. If within the above range, a highly uniform coating film is easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to coat with the film thickness required for reinsertion insulation. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[0623] <Restrictions on the Contents of Resin Compositions>

[0624] The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0625] Methods for maintaining moisture content include adjusting humidity in storage conditions and reducing the porosity of the storage container.

[0626] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, excluding metals contained in the form of complexes between organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-described range.

[0627] Furthermore, as a method for reducing unintentionally contained metallic impurities in the resin composition of the present invention, examples include: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and performing distillation under conditions that suppress contamination as much as possible by lining the device with polytetrafluoroethylene or the like.

[0628] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the content of halogen atoms 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. Of this, the content present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. Preferably, the total amount of chlorine atoms and bromine atoms, or the total amount of chloride ions and bromide ions, is within the above-mentioned ranges.

[0629] Methods for adjusting the content of halogen atoms include, preferably, ion exchange treatment.

[0630] As a container for the resin composition of the present invention, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with the inner wall composed of six layers of six different resins or bottles with the six resins formed into a seven-layer structure are also preferred. Examples of such containers include those described in Japanese Patent Application Publication No. 2015-123351.

[0631] <Cureds of Resin Compositions>

[0632] By curing the resin composition of the present invention, a cured resin composition can be obtained.

[0633] The cured product of the present invention is a cured product obtained by curing a resin composition.

[0634] The curing of the resin composition is preferably carried out by heating, with a heating temperature more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in film form. Through patterning of the resin composition, the shape of the cured product can also be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0635] The shrinkage rate during curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated according to the following formula.

[0636] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0637] <Characteristics of cured resin compositions>

[0638] The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[0639] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0640] The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0641] <Preparation of Resin Compositions>

[0642] The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0643] Examples of mixing methods include mixing based on stirring blades, mixing based on ball mills, and mixing by rotating a tank.

[0644] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0645] For the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration is preferably performed using a filter. The filter pore size is preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter that has been pre-cleaned with an organic solvent. Multiple filters can be connected in series or in parallel during the filtration process. When using multiple filters, filters with different pore sizes or materials can be used in combination. For example, a connection method can be used where a 1 μm pore size HDPE filter is used as the first stage, and a 0.2 μm pore size HDPE filter is used as the second stage, and the two are connected in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, cyclic filtration can be performed. Furthermore, filtration can be performed by pressurization. When filtration is performed by pressurization, the applied pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0646] Besides using filters for filtration, adsorption materials can also be used to remove impurities. Filtration and impurity removal using adsorption materials can also be combined. Known adsorption materials can be used. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0647] Alternatively, after filtration using a filter, the resin composition filled in the bottle can be degassed under reduced pressure.

[0648] (Method for manufacturing solidified products)

[0649] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0650] The method for manufacturing the cured material more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[0651] The method for manufacturing the cured material is particularly preferably one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[0652] Furthermore, the method for manufacturing the cured material preferably includes the above-mentioned film formation step and the step of heating the above-mentioned film.

[0653] The following is a detailed explanation of each process.

[0654] <Membrane Formation Process>

[0655] The resin composition of the present invention can be used in a film forming process applicable to a substrate for forming a film.

[0656] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

[0657] [Substrate]

[0658] The type of substrate can be appropriately determined according to the application and is not particularly limited. In particular, semiconductor manufacturing substrates are preferred, and silicon substrates, Cu substrates, and molding substrates are more preferred.

[0659] When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer composed of cured material) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0660] As a method for applying a resin composition to a substrate, coating is preferred.

[0661] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred; from both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the applicable method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0662] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a temporary support through the above-described application method onto a substrate.

[0663] Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 is preferably used.

[0664] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0665] A pre-wetting process can be adopted, in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, followed by the application of the resin composition.

[0666] <Drying Process>

[0667] After the film formation process (layer formation process), the above-mentioned film can be supplied to a process for drying the formed film (layer) (drying process) to remove the solvent.

[0668] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[0669] The drying process described above is preferably performed after the film formation process and before the exposure process.

[0670] The drying temperature of the membrane in the drying process is preferably 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. Furthermore, drying can be carried out under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0671] <Exposure Process>

[0672] The above-mentioned film can be used in an exposure process for selective exposure of the film.

[0673] The method for manufacturing a cured material may include an exposure process that selectively exposes a film formed by a film forming process.

[0674] Selective exposure refers to exposing only a portion of the film. Furthermore, by selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film.

[0675] Regarding the exposure amount, it is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[0676] The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0677] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (gamma, h, and i-ray wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is preferred, and from the viewpoint of exposure sensitivity, exposure based on i-rays is more preferred.

[0678] The exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask, exposure based on laser direct imaging, etc.

[0679] <Post-exposure heating process>

[0680] The above-mentioned film can be used in the process of heating after exposure (post-exposure heating process).

[0681] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0682] The post-exposure heating process can be performed after the exposure process and before the development process.

[0683] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0684] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0685] From the initial heating temperature to the maximum heating temperature, the heating rate during the post-exposure heating process is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0686] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0687] As a heating mechanism in the post-exposure heating process, it is not particularly limited and can use known heating plates, ovens, infrared heaters, etc.

[0688] Furthermore, when heating, it is preferable to carry out the process in an atmosphere with low oxygen concentration by introducing inert gases such as nitrogen, helium, or argon.

[0689] <Developing Process>

[0690] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[0691] That is, the method for manufacturing the cured material of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[0692] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[0693] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[0694] [Developing solution]

[0695] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0696] When the developer is an alkaline aqueous solution, the alkaline compound that may be contained in the alkaline aqueous solution is a compound described in paragraph 0256 of International Publication No. 2023 / 190062, preferably TMAH. The content of the alkaline 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.

[0697] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated herein by reference. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferably listed as alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably listed as amides.

[0698] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, a developer containing at least one selected from cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred; a developer containing at least one selected from cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is particularly preferred.

[0699] 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. Furthermore, the above content can also be 100% by mass.

[0700] When the developer contains an organic solvent, it may also contain at least one of an alkaline compound and an alkali-generating agent. The penetration of at least one of the alkaline compound and alkali-generating agent into the pattern in the developer can sometimes improve properties such as the elongation at break of the pattern.

[0701] From the viewpoint of reliability when remaining on the cured film (adhesion to the substrate when the cured material is further heated), organic bases are preferred as alkaline compounds.

[0702] As a basic compound, a basic compound having an amino group is preferred, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. To promote the imidization reaction, a primary amine, secondary amine, tertiary amine or ammonium salt is preferred, more preferably a secondary amine, tertiary amine or ammonium salt, even more preferably a secondary amine or tertiary amine, and especially preferably a tertiary amine.

[0703] From the viewpoint of the mechanical properties (elongation at break) of the cured product, compounds that are not easily retained in the cured film (the obtained cured product) are preferred as alkaline compounds. From the viewpoint of promoting cyclization, compounds whose residual amount is not easily reduced by vaporization or the like before heating are preferred.

[0704] Therefore, the boiling point of the alkaline compound is preferably 30°C to 350°C at atmospheric pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C.

[0705] The boiling point of the alkaline compound is preferably higher than the temperature obtained by subtracting 20°C from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[0706] For example, when the boiling point of the organic solvent is 100°C, the boiling point of the alkaline compound used is preferably 80°C or higher, and more preferably 100°C or higher.

[0707] The developer may contain only one basic compound or more than two.

[0708] As a specific example of a basic compound, the compound described in paragraph 0262 of International Publication No. 2023 / 190062 can be cited.

[0709] The preferred method for the alkali-generating agent is the same as that for the alkali-generating agent contained in the above-described composition. In particular, the alkali-generating agent is preferably a thermal alkali-generating agent.

[0710] When the developer contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more.

[0711] When the alkaline compound or alkali-generating agent is solid in the environment of using the developer, it is even more preferable that the content of the alkaline compound or alkali-generating agent is 70 to 100% by mass relative to the total solid content of the developer.

[0712] The developer may contain only one of the basic compound and the alkali-generating agent, or it may contain two or more of them. When there are two or more of the basic compound and the alkali-generating agent, it is preferable that their total amount is within the range described above.

[0713] The developer may further contain other ingredients.

[0714] Other components include, for example, well-known surfactants or well-known defoamers.

[0715] [Method for supplying developer]

[0716] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include immersing the substrate with the film formed in the developer, swirling immersion development using a nozzle to supply the developer to the film formed on the substrate, or continuous supply of developer. There are no particular restrictions on the type of nozzle, such as straight nozzles, shower nozzles, and spray nozzles.

[0717] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to use a method of supplying developer using a straight nozzle or a method of continuous supply using a spray nozzle. From the viewpoint of developer penetration into the image area, it is more preferable to use a method of supplying developer using a spray nozzle.

[0718] Furthermore, the process can be performed by continuously supplying developer using a straight nozzle, rotating the substrate to remove developer from the substrate, performing rotary drying, continuously supplying developer again using a straight nozzle, and rotating the substrate to remove developer from the substrate, and this process can be repeated multiple times.

[0719] Methods for supplying developer in the developing process include processes such as continuously supplying developer to a substrate, maintaining developer on a substrate in a substantially static state, using ultrasound or the like to vibrate developer on a substrate, and combining these methods.

[0720] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[0721] In the developing process, after treatment with the developing solution, the pattern can be further cleaned (rinsed) with a rinsing solution. Furthermore, methods such as supplying the rinsing solution before the developing solution in contact with the pattern has completely dried can be employed.

[0722] [Rinse solution]

[0723] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0724] Regarding the flushing fluid, please refer to paragraphs 0270 to 0280 of International Publication No. 2023 / 190062.

[0725] <Heating Process>

[0726] The pattern obtained by the developing process (or the washed pattern if a rinsing process is performed) can be used in a heating process for heating the pattern obtained by the developing process described above.

[0727] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[0728] Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[0729] During the heating process, resins such as polyimide precursors are cyclized to become resins such as polyimide.

[0730] Furthermore, crosslinking of unreacted crosslinking groups in a specific resin or a crosslinking agent other than a specific resin is also performed.

[0731] The heating temperature (maximum heating temperature) in the heating process is preferably 50-450°C, more preferably 150-350°C, even more preferably 150-250°C, even more preferably 160-250°C, and especially preferably 160-230°C.

[0732] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by heating and by the action of the alkali or the like generated by the alkali generating agent.

[0733] From the initial heating temperature to the maximum heating temperature, the heating process is preferably carried out at a heating rate of 1 to 12°C / minute. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, excessive evaporation of acid or solvent can be prevented while ensuring productivity, and by setting the heating rate to 12°C / minute or less, residual stress in the cured product can be mitigated.

[0734] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0735] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, in the case of applying the resin composition of the present invention to a substrate and then drying it, it is the temperature of the dried film (layer), preferably starting at a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0736] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0737] In particular, when forming a multi-layered laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0738] The upper limit of the above heating temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0739] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, and then heating from 120°C to 180°C at a rate of 2°C / min, holding at 180°C for 120 minutes. Furthermore, it is preferable to perform the treatment while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. This pretreatment process can improve the properties of the membrane. The pretreatment process only needs to be performed for a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a two-stage or more process; for example, the first stage of the pretreatment process can be performed in the range of 100–150°C, followed by the second stage of the pretreatment process in the range of 150–200°C.

[0740] Alternatively, heating followed by cooling can be performed. In this case, a cooling rate of 1 to 5°C / minute is preferred.

[0741] Regarding the heating process, from the viewpoint of preventing the decomposition of specific resins, it is preferable to carry it under reduced pressure by introducing inactive gases such as nitrogen, helium, or argon, thereby creating an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0742] As a heating mechanism in the heating process, it is not particularly limited, and examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0743] <Post-development exposure process>

[0744] The pattern obtained by the developing process (or the washed pattern in the case of a washing process) can be used in a post-developing exposure process to expose the pattern after the developing process, instead of the heating process described above or in addition to the heating process described above.

[0745] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

[0746] In the post-development exposure process, it can promote, for example, the cyclization reaction of polyimide precursors by photosensitive alkali generating agents, and the removal of acid-decomposing groups by photosensitive acid generating agents.

[0747] In the post-development exposure process, it is sufficient for at least a portion of the pattern obtained in the development process to be exposed, preferably all of the pattern is exposed.

[0748] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0749] The post-development exposure process can be performed using the light source described in the above-mentioned exposure process, preferably broadband light.

[0750] <Metal Layer Formation Process>

[0751] The pattern obtained by the developing process (preferably a pattern obtained by at least one of a heating process and a post-development exposure process) can be used in a metal layer forming process to form a metal layer on the pattern.

[0752] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably a pattern obtained by at least one of a heating step and a post-developing exposure step).

[0753] As a metal layer, it is not particularly limited and can use existing metal types, such as 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.

[0754] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7,888,181B2, and US Patent No. 9,177,926B2 can be used. For example, photolithography, PVD (physical 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 listed. As a preferred method of plating, electroplating using copper sulfate or copper cyanide plating solutions can be listed.

[0755] The thickness of the metal layer, measured in the thickest portion, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[0756] <Uses>

[0757] Examples of fields in which the manufacturing method or cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Furthermore, examples include patterning of sealing films, substrate materials (bottom or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for mounting purposes as described above, by etching. For their applications, please refer to, for example, SCIENCE AND TECHNOLOGY CO.,LTD. "High Functionalization and Applicable Technology of Polyimide," 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, edited "Latest Polyimide Fundamentals and Applications," NTS Inc., August 2010.

[0758] The method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, in the etching of molded parts, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0759] (Laminated bodies and methods for manufacturing laminated bodies)

[0760] The laminate of the present invention refers to a structure having multiple layers composed of the cured material of the present invention.

[0761] A laminate is a laminate containing two or more layers of solidified material, or it can be a laminate containing three or more layers.

[0762] In the above-mentioned laminate, at least one of the two or more layers composed of cured material is a layer composed of the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material that occurs with the shrinkage, it is even more preferable that all the layers composed of cured material in the above-mentioned laminate are composed of the cured material of the present invention.

[0763] That is, the method for manufacturing the laminate of the present invention preferably includes the 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.

[0764] The laminate of the present invention preferably comprises two or more layers made of cured material, and a metal layer is included between any of the layers made of cured material. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0765] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between multiple methods for manufacturing cured products, wherein a metal layer is formed on the layer composed of the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0766] As an example of the aforementioned laminate, a laminate structure comprising at least three layers sequentially stacked together, namely a layer composed of a first cured material, a metal layer, and a layer composed of a second cured material, may be preferred.

[0767] Preferably, both the layer composed of the first cured product and the layer composed of the second cured product are layers composed of the cured products of the present invention. The resin composition of the present invention used to form the layer composed of the first cured product and the resin composition of the present invention used to form the layer composed of the second cured product can be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0768] <Layering Process>

[0769] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0770] The lamination process includes a series of steps that sequentially perform at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step on the surface of a pattern (resin layer) or a metal layer. Alternatively, at least one of (a) the film formation step, (d) the heating step, and the post-development exposure step may be repeated. Furthermore, (e) the metal layer formation step may be included after at least one of (d) the heating step and the post-development exposure step. Of course, the lamination process may further appropriately include the aforementioned drying step, etc.

[0771] If a further lamination process is performed after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned heating process, or the aforementioned metal layer formation process. Plasma treatment can be cited as an example of surface activation treatment. Details regarding surface activation treatment will be described later.

[0772] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0773] For example, a structure with 2 or more but less than 20 resin layers is preferred, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and a structure with 2 or more but less than 9 resin layers is even more preferred.

[0774] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0775] In this invention, it is particularly preferred to form a cured product (resin layer) of the resin composition of the present invention by covering the metal layer after the metal layer is formed. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order, or repeating at least one of (a) film formation step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order. By alternately performing the lamination step of 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 laminated.

[0776] (Surface activation treatment process)

[0777] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.

[0778] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the resin composition layer.

[0779] The surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, at least a portion of the metal layer is subjected to surface activation treatment; more preferably, a portion or all of the region of the metal layer on which the resin composition layer is formed is subjected to surface activation treatment. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved.

[0780] It is also preferable to perform surface activation treatment on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. Especially in cases where the resin composition layer has cured, such as during negative development, it is less susceptible to damage caused by surface treatment, and adhesion is easily improved.

[0781] Regarding surface activation treatment, it can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0782] (Semiconductor devices and their manufacturing methods)

[0783] The present invention also discloses a semiconductor device comprising the cured material or laminate of the present invention.

[0784] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product or the method for manufacturing a laminate of the present invention.

[0785] As a specific example of using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer in a semiconductor device, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description in FIG1, which are incorporated herein by reference.

[0786] Example

[0787] The following examples provide a more detailed description of the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" refer to mass measurements.

[0788] <Examples and Comparative Examples>

[0789] In each embodiment and comparative example, the components described in Tables 1 to 13 below were mixed to obtain each resin composition.

[0790] Specifically, the content of each component other than the solvent recorded in the table is set as the amount (parts by mass) recorded in the "parts by mass" row.

[0791] When using two or more compounds as resins, the columns for "Resin Structure," "Condensing Agent," "Mw (weight-average molecular weight) of Resin," "Imidification Rate (%)," and "Parts by Mass" should be separated by " / ". The order in which these columns are separated by " / " corresponds accordingly. When two or more components other than resins are included, the amount of the component recorded in the "Type" line is the "Parts by Mass" recorded in the next line (i.e., the line immediately following the "Type" line).

[0792] The amount of solvent used was adjusted to be the same as the solid content concentration (mass%) recorded in each table.

[0793] Each table lists the "type" and "ratio" of the solvents used. The "ratio" of a solvent is the percentage (by mass) of each type of solvent relative to the total solvent. When more than two solvents are included, the ratio of the solvent listed in the "type" row is the same as the ratio listed in the next row (i.e., the row immediately following the "type" row).

[0794] In each table, a "-" indicates that the resin composition does not contain that component.

[0795] The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[0796] The detailed information of each component recorded in each table is as follows.

[0797] [Resin]

[0798] The structure of the resins used is shown below (resin structure). Each resin contains repeating units enclosed in square brackets []. For resins containing two repeating units, the content of each repeating unit (the molar ratio (mol%) relative to all repeating units) is indicated below to the right of its respective square brackets [].

[0799] In the structural formula of resin 3, R is a group represented by RX1 or RX2, and the molar ratio of RX1 / RX2 is 50 / 50.

[0800] The Mw and imidization rate of the resins used in each example and comparative example are described in the table. Regarding Mw, it was determined by sequentially connecting the guard columns SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by TOSOHCORPORATION) in series. The eluent was determined using NMP (N-methyl-2-pyrrolidone).

[0801] Resins 1 to 12 are polyamic acid esters, and resins 13 to 16 are polyimides.

[0802] Resins 1 to 12 are resins obtained by polymerization reactions using carboxylic anhydrides and diamines corresponding to the structures described therein as raw materials and the "condensing agent" listed in the table as an activator for the amidation reaction. The DCC used as the condensing agent is dicyclohexylcarbodiimide. Furthermore, when "SOCl2" is listed in the "condensing agent" column, SOCl2 (thionyl chloride) is used. Although SOCl2 is a halogenating agent rather than a condensing agent, it is listed in the "condensing agent" column in the table for convenience.

[0803] Resin 1 to Resin 16 are all insoluble in alkaline aqueous solutions (i.e., the mass of soluble in 100g of 2.38% tetramethylammonium aqueous solution at 23°C is less than 0.1g).

[0804] [Chemical Formula 29]

[0805]

[0806] [Chemical Formula 30]

[0807]

[0808] [Chemical Formula 31]

[0809]

[0810] [Chemical Formula 32]

[0811]

[0812] [Chemical Formula 33]

[0813]

[0814] [Chemical Formula 34]

[0815]

[0816] [Chemical Formula 35]

[0817]

[0818] [Chemical Formula 36]

[0819]

[0820] [Chemical Formula 37]

[0821]

[0822] [Chemical Formula 38]

[0823]

[0824] [Chemical Formula 39]

[0825]

[0826] [Chemical Formula 40]

[0827]

[0828] [Chemical Formula 41]

[0829]

[0830] [Chemical Formula 42]

[0831]

[0832] [Chemical Formula 43]

[0833]

[0834] [Chemical Formula 44]

[0835]

[0836] [Monofunctional Monomer]

[0837] The structure of the monofunctional monomer used is shown below.

[0838] [Chemical Formula 45]

[0839]

[0840] A-7 to A-12 are represented by the aforementioned formula (a1), and R in formula (a1) 2 Compounds that represent organic groups.

[0841] The following shows the R in A-7 to A-122 The structure and molecular weight of the organic group represented. R 2 (A-7) ~ R 2 (A-12) represent the options from A-7 to A-12 derived from R. 2 The organic group is represented.

[0842] [Chemical Formula 46]

[0843]

[0844] Furthermore, the structures of the components other than those mentioned above are shown below.

[0845] [Chemical Formula 47]

[0846]

[0847] [Chemical Formula 48]

[0848]

[0849] I-1 to I-7 are photopolymerization initiators.

[0850] [Chemical Formula 49]

[0851]

[0852] [Chemical Formula 50]

[0853]

[0854] [Chemical Formula 51]

[0855]

[0856] [Chemical Formula 52]

[0857]

[0858] [Chemical Formula 53]

[0859]

[0860] “DPHA” stands for dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)).

[0861] “E-7” is an ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid.

[0862] "E-8" is a diazonoquinone compound synthesized by the following method.

[0863] <Synthesis of E-8>

[0864] 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.: Tris-PA) was added to a flask. Next, 46.93 g (174.9 mmol) of 1,2-diazonaphthol-5-sulfonyl chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring. The solution was added dropwise to the flask over 30 minutes using a dropping funnel, and the mixture was stirred at an internal temperature of 30°C for 30 minutes. Then, hydrochloric acid was added dropwise, and the mixture was stirred for another 30 minutes. Next, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker. The filtrate obtained by filtering the hydrochloride salt from the reaction solution was added dropwise to this solution. The precipitate was filtered, washed with water, and dried under vacuum at 40°C for 50 hours to obtain the diazononaphthoquinone compound E-8.

[0865] [Solvent]

[0866] NMP: N-methyl-2-pyrrolidone

[0867] ·EL: Ethyl lactate

[0868] DMSO: Dimethyl sulfoxide

[0869] GBL: γ-Butyrolactone

[0870] GVL: γ-valerolactone

[0871] • MDMPA: 3-Methoxy-N,N-Dimethylpropionamide (KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.))

[0872] Toluene: Toluene

[0873] ·CP: Cyclopentanone

[0874] CH: Cyclohexanone

[0875] [Focusing on the evaluation of margin]

[0876] The photosensitive resin compositions prepared in each example and comparative example were coated onto an 8-inch silicon wafer using a spin-coating method to form a coating film. The silicon wafer with the obtained coating film was dried on a hot plate at 100°C for 5 minutes, thereby forming a uniform resin composition layer (photosensitive film) with a thickness of 6 μm on the silicon wafer.

[0877] Exposure was performed on the resin composition layer using a circular mask with a diameter of 3 μm. The focal point of the exposure light was moved 0.5 μm at a time from the film surface toward the bottom of the film. The exposure wavelength was set to the wavelength listed in the "Exposure Wavelength (nm)" column of the table.

[0878] In the example where the exposure condition is marked as "M", a stepper was used as the light source for the exposure.

[0879] In the example where the exposure condition is marked as "D", a direct exposure device (ADTEC DE-6UH III) was used as the light source, and direct laser imaging exposure was performed within a circular area with a diameter of 5μm without the use of a photomask.

[0880] After exposure, the wafer is placed on the horizontal rotating stage of a rotary / spray developer (DW-30 type; manufactured by CHEMITRONICS CO.,LTD.), and cyclopentanone is used as the developer. The development is carried out at 23°C for 60 seconds to remove the unexposed areas and form a pattern.

[0881] The exposed resin composition layer (resin layer) is heated at a rate of 10°C / min under a nitrogen atmosphere. In the example where a value is recorded in the "Curing Temperature (°C)" column, the exposed resin composition layer is heated using a heating plate at a rate of 10°C / min under a nitrogen atmosphere until the temperature recorded in the "Curing Temperature (°C)" column of the table is reached. This temperature is then maintained for the time (minutes) recorded in the "Curing Time (min)" column of the table to obtain a cured product.

[0882] In the example where "IR" is listed in the "Curing Temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCERIKO, Inc., RTP-6) was used to heat the obtained resin composition layer under a nitrogen atmosphere at a heating rate of 10°C / min until it reached 230°C. This temperature was then maintained for the time specified in the "Curing Time (min)" table to obtain the cured product.

[0883] For each cured product, the pattern shape or width of the patterned area was observed under an optical microscope. The length of the range of movement of the focal point of the exposure light that forms the desired pattern along the film thickness direction was used as the focus margin, and the results were evaluated according to the following criteria. The evaluation results are recorded in the "Focus Margin" column of the table. A desired pattern was considered to have been formed when the angle between the bottom surface and the side of the pattern was 80–100° and the pattern diameter was 2.7–3.3 μm. A larger focus margin value indicates better focus margin and is considered the preferred result.

[0884] -Evaluation Criteria-

[0885] A: The focusing margin is above 12μm.

[0886] B: Focusing margin is greater than 8μm and less than 12μm.

[0887] C: Focus margin greater than 5μm and less than 8μm.

[0888] D: Focusing margin is below 5μm.

[0889] [Table 1]

[0890]

[0891] [Table 2]

[0892]

[0893] [Table 3]

[0894]

[0895] [Table 4]

[0896]

[0897] [Table 5]

[0898]

[0899] [Table 6]

[0900]

[0901] [Table 7]

[0902]

[0903] [Table 8]

[0904]

[0905] [Table 9]

[0906]

[0907] [Table 10]

[0908]

[0909] [Table 11]

[0910]

[0911] [Table 12]

[0912]

[0913] [Table 13]

[0914]

[0915] The results above show that the resin composition of the present invention has excellent focusing margin.

[0916] <Example 201>

[0917] The photosensitive resin composition used in Example 1 was spin-coated onto the copper layer surface of a resin substrate with a copper layer formed thereon. After drying at 100°C for 4 minutes to form a 20 μm thick film, exposure was performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-to-space pattern and a linewidth of 10 μm). After exposure, the film was heated at 100°C for 4 minutes. Following the heating, the film was developed in cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.

[0918] Next, the temperature was increased at a rate of 10°C / min under nitrogen atmosphere, and after reaching 230°C, it was maintained at 230°C for 3 hours, thereby forming an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer has excellent insulation properties.

[0919] Furthermore, semiconductor devices were fabricated using these rewiring layers with interlayer insulating films, and normal operation was confirmed.

[0920] Industrial availability

[0921] According to the present invention, a method for manufacturing a photosensitive resin composition with excellent focusing margin and a cured product is provided.

[0922] The present invention has been described in detail with reference to specific embodiments, but those skilled in the art should know that various changes or modifications can be made without departing from the spirit and scope of the present invention.

[0923] This application is based on Japanese Patent Application No. 2023-192452, filed on November 10, 2023, the contents of which are incorporated herein by reference.

Claims

1. A photosensitive resin composition comprising: Polyimide; Compound (S1) has only one (meth)acryloyl group in its molecule; and Photopolymerization initiator.

2. The photosensitive resin composition according to claim 1, wherein, The compound (S1) is 2-hydroxyethyl methacrylate.

3. The photosensitive resin composition according to claim 1, wherein, The polyimide is insoluble in alkaline aqueous solutions.

4. A photosensitive resin composition comprising: Polyamide ester; Compound (S2), having only one (meth)acryloyl group in its molecule and represented by the following formula (a1); and Photopolymerization initiator, In formula (a1), R 1 Indicates a hydrogen atom or a methyl group. L 1 Indicates a divalent linkage group. X 1 Indicates -NR N1 -、-O- or -S-, R N1 Indicates a hydrogen atom or an organic group. R 2 Indicates a hydrogen atom or an organic group. R 2 With L 1 They can be bonded arbitrarily to form rings. R 2 With R N1 They can be bonded arbitrarily to form a ring.

5. The photosensitive resin composition according to claim 4, wherein, R in equation (a1) 2 It represents a hydrogen atom.

6. The photosensitive resin composition according to claim 4, wherein, R in equation (a1) 2 This indicates an organic group with a molecular weight of less than 133.

0.

7. The photosensitive resin composition according to claim 4, wherein, The compound (S2) is 2-hydroxyethyl methacrylate.

8. The photosensitive resin composition according to claim 4, wherein, The polyamic acid ester is insoluble in alkaline aqueous solutions.

9. The photosensitive resin composition according to claim 4, wherein, The polyamic acid ester contains groups having olefinically unsaturated bonds.

10. A photosensitive resin composition comprising: Polyamide ester; Compound (S3), having only one (meth)acryloyl group in its molecule and represented by the following formula (a2); and Photopolymerization initiator, In equation (a2), R 3 Indicates a hydrogen atom or a methyl group. X 2 Indicates -NR N2 -or-O-, R N2 Indicates a hydrogen atom or an organic group. R 4 Indicates an aryl group or an alkyl group having 3 or more carbon atoms. R 4 With R N2 They can be bonded arbitrarily to form a ring.

11. The photosensitive resin composition according to claim 10, wherein, The polyamic acid ester is insoluble in alkaline aqueous solutions.

12. The photosensitive resin composition according to claim 10, wherein, The polyamic acid ester contains groups having olefinically unsaturated bonds.

13. The photosensitive resin composition according to any one of claims 1 to 12, used for forming an insulating film for a rewiring layer.

14. A method for manufacturing a cured material, comprising: The film forming process involves applying the photosensitive resin composition according to any one of claims 1 to 12 onto a substrate to form a film; The exposure process selectively exposes the film formed through the film formation process. and The developing process involves using a developing solution to develop the film exposed in the exposure process to form a pattern.

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