Resin composition, resin sheet, multilayer printed circuit board, and semiconductor device

Abstract

To provide a resin composition, a resin sheet, a multilayer printed circuit board, and a semiconductor device, which do not hinder a photocuring reaction in an exposure step when a multilayer printed circuit board is manufactured, and which can impart excellent alkali developability in a development step. The resin composition of the present invention contains a compound (A) represented by the following formula (1), and a compound (B) containing one or more carboxyl groups other than the compound (A) represented by the following formula (1). (In formula (1), each of R1 independently represents a group represented by the following formula (2) or a hydrogen atom. Each of R2 independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. At least one of R1 is a group represented by the following formula (2).) (In formula (2), * represents an atomic bond.)

Description

Technical Field

[0001] This invention relates to resin compositions, resin sheets, multilayer printed circuit boards, and semiconductor devices. Background Technology

[0002] Due to the miniaturization and high density of multilayer printed circuit boards (PCBs), research is actively underway to reduce the thickness of the laminates used in multilayer PCBs. Along with this thinning, there is also a demand for thinner insulating layers, leading to the search for resin sheets that do not contain glass cloth. Regarding the resin compositions used as insulating layers, thermosetting resins are the mainstream choice, and the openings used to create conductivity between insulating layers are typically achieved through laser processing.

[0003] On the other hand, laser-processed openings have the following problems: the more holes a high-density substrate has, the longer the processing time becomes. Therefore, in recent years, there has been a demand for resin sheets that use a resin composition that can cure the exposed areas (exposure process) and remove the unexposed areas (development process) by irradiation with light or the like, thereby enabling opening processing to be performed in one step through the exposure and development processes.

[0004] As an exposure method, a method using a mercury lamp as a light source and exposing the material through a photomask is employed, requiring materials that can be appropriately exposed under the light source of the mercury lamp. This mercury lamp-based exposure method uses mixed gamma rays (gamma rays with a wavelength of 436 nm, h-rays with a wavelength of 405 nm, and i-rays with a wavelength of 365 nm), and a generally applicable photocurable initiator can be selected. In recent years, the introduction of a direct drawing exposure method, where pattern-based digital data is directly drawn onto a photosensitive resin composition layer without the need for a photomask, has also been progressing. Compared to exposure methods using a photomask, this direct drawing exposure method offers better positional alignment accuracy and can produce highly detailed patterns; therefore, its adoption is particularly advanced in substrates requiring high-density wiring. This light source uses monochromatic light such as lasers, and in DMD (Digital Micromirror Device) devices capable of forming highly detailed resist patterns, a light source with a wavelength of 405 nm (h-rays) is used.

[0005] As a developing method, alkaline development was used to obtain highly detailed patterns.

[0006] Patent Document 1 describes a resin composition comprising a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition used in laminates and resin sheets.

[0007] Furthermore, Patent Document 2 describes a resin composition comprising: a multi-carboxyl-containing compound obtained by reacting bismaleimide with a monoamine followed by reacting with an acid anhydride, and a curable resin such as an epoxy resin. Additionally, Patent Document 2 describes a multi-carboxyl-containing compound capable of producing a cured product with alkali-developable properties.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: WO2018 / 56466A1

[0011] Patent Document 2: Japanese Patent Application Publication No. 2015-229734 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] However, in Patent Document 1, a bismaleimide compound is used as the curing resin. But maleimide compounds typically have poor light transmittance. Therefore, if a maleimide compound is included, light cannot sufficiently reach the photocuring initiator, making it difficult for the initiator to generate free radicals, resulting in very low reactivity. Therefore, in Patent Document 1, the maleimide compound is cured by additional heating before development. However, due to the accompanying heating, a high-precision resist pattern cannot be obtained. Furthermore, the resin composition described in Patent Document 1 originally has insufficient alkaline developability, resulting in unexposed resin composition residue after development. Therefore, from this perspective, a high-precision resist pattern cannot be obtained in Patent Document 1, making it unsuitable for manufacturing high-density printed circuit boards.

[0014] Furthermore, the multi-carboxyl compound described in Patent Document 2 requires a complex process involving the reaction of bismaleimide with a monoamine followed by an acid anhydride reaction. Additionally, the use of an aromatic amine compound as the monoamine results in the multi-carboxyl compound containing an amide group with an aromatic ring in its structure. Consequently, this multi-carboxyl compound is practically unsuitable for use in photosensitive resin compositions due to its poor light transmittance and hindrance to photocuring reactions.

[0015] Therefore, the present invention was made in view of the problems of this prior art, and provides a resin composition, resin sheet, multilayer printed circuit board and semiconductor device that do not hinder the photocuring reaction in the exposure process when used to manufacture multilayer printed circuit boards and can impart excellent alkaline developability in the development process.

[0016] Solution for solving the problem

[0017] The inventors conducted in-depth research and discovered that by using a resin composition containing a specific carboxyl-containing compound (A) and a compound (B) containing one or more carboxyl groups other than compound (A) in the exposure and development processes of manufacturing multilayer printed circuit boards, it is possible to obtain a cured product without hindering the photocuring reaction and to impart excellent alkaline developability to the resin composition, thereby completing the present invention.

[0018] That is, the present invention includes the following contents.

[0019] [1] A resin composition comprising:

[0020] The compound (A) shown in formula (1) below; and

[0021] Compounds (B) containing one or more carboxyl groups, other than compound (A) shown in formula (1) below.

[0022]

[0023] (In formula (1), each R1 independently represents a group or hydrogen atom as shown in formula (2) below. Each R2 independently represents a hydrogen atom, or a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms. Among them, at least one R1 is a group as shown in formula (2) below.)

[0024]

[0025] (In equation (2), -* represents an atomic bond.)

[0026] [2] According to the resin composition of [1], wherein, in the aforementioned formula (1), at least one of the aforementioned R1 is a group represented by the following formula (3).

[0027]

[0028] (In equation (3), -* represents an atomic bond.)

[0029] [3] The resin composition according to [1] or [2] further comprises a maleimide compound (C).

[0030] [4] The resin composition according to any one of [1] to [3] further comprises a photocuring initiator (D).

[0031] [5] The resin composition according to any one of [1] to [4], wherein the aforementioned compound (B) containing one or more carboxyl groups comprises at least one of the group consisting of anhydrides of fully hydrogenated aromatic polycarboxylic acids, anhydrides of partially hydrogenated aromatic polycarboxylic acids, and acid-modified epoxy (meth)acrylates.

[0032] [6] According to the resin composition of [3], wherein the aforementioned maleimide compound (C) comprises a bismaleimide compound (C1), the bismaleimide compound (C1) comprising a structural unit as shown in the following formula (4) and maleimide groups located at both ends of the molecular chain.

[0033]

[0034] (In formula (4), R3 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. R4 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. R5 each independently represents a hydrogen atom, a straight-chain alkyl or branched alkyl with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. n1 each independently represents an integer from 1 to 10.)

[0035] [7] A resin sheet having a support and a resin layer disposed on one or both sides of the support, the resin layer comprising any one of [1] to [6].

[0036] [8] The resin sheet according to [7], wherein the thickness of the aforementioned resin layer is 1 to 50 μm.

[0037] [9] A multilayer printed circuit board having an insulating layer and a conductor layer formed on one or both sides of the insulating layer, wherein the insulating layer comprises any one of [1] to [6].

[0038]

[10] A semiconductor device comprising any one of the resin compositions described in [1] to [6].

[0039] The effects of the invention

[0040] According to the resin composition of the present invention, in the exposure and development processes of manufacturing multilayer printed circuit boards, a cured product can be appropriately obtained without hindering the photocuring reaction, and excellent alkaline developability can be imparted. Attached Figure Description

[0041] Figure 1 It is an amyl acid compound (MA-TMDA) 1 1H-NMR spectrum.

[0042] Figure 2 It is a maleimide compound (TMDM) 1 1H-NMR spectrum.

[0043] Figure 3It is the compound (A-1) obtained in Synthesis Example 2. 1 1H-NMR spectrum. Detailed Implementation

[0044] Hereinafter, a detailed description will be given of a method for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to its contents. The present invention can be implemented with appropriate modifications within the scope of this spirit.

[0045] It should be noted that in this specification, "(meth)acrylic acid" refers to both "acrylic acid" and its corresponding "methacrylic acid," "(meth)acrylate" refers to both "acrylate" and its corresponding "methacrylate," and "(meth)acryloyl" refers to both "acryloyl" and its corresponding "methacryloyl." Furthermore, in this specification, "solid resin components" or "solid resin components in the resin composition," unless otherwise specified, refers to the components in the resin composition other than compound (A), compound (B), photocuring initiator (D), additives, solvents, and fillers. "100 parts by weight of solid resin components" means that the total amount of components in the resin composition other than compound (A), compound (B), photocuring initiator (D), additives, solvents, and fillers is 100 parts by weight.

[0046] In this specification, Mw represents the mass-average molecular weight, Mn represents the number-average molecular weight, and Mw / Mn represents the molecular weight distribution. Mw, Mn, and Mw / Mn can be determined by gel permeation chromatography (GPC) using polystyrene standards.

[0047] [Resin Composition]

[0048] The resin composition of this embodiment comprises compound (A) of formula (1) (also called component (A) or compound (A)) and compound (B) (also called component (B) or compound (B)) containing one or more carboxyl groups other than compound (A) of formula (1). The resin composition of this embodiment, comprising compound (A) and compound (B), is suitable for use in the fabrication of multilayer printed circuit boards. By using the resin composition, a cured product can be suitably obtained in the exposure and development processes of fabricating multilayer printed circuit boards without hindering the photocuring reaction, and excellent alkaline developability can be imparted after exposure.

[0049] [Compound (A)]

[0050] The resin composition of this embodiment comprises compound (A) as shown in formula (1).

[0051]

[0052] In formula (1), each R1 independently represents a group or hydrogen atom as shown in formula (2), and each R2 independently represents a hydrogen atom, or a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms. Among them, at least one R1 is a group as shown in formula (2).

[0053]

[0054] In equation (2), -* represents the atomic bond that connects to the oxygen atom (O) directly connected to R1 in equation (1).

[0055] In this embodiment, during the exposure and development processes of manufacturing a multilayer printed circuit board, by using a resin composition that contains both compound (A) and compound (B) (described later), a cured product can be suitably obtained without hindering the photocuring reaction. Furthermore, excellent alkaline developability can be imparted to the resin composition in the unexposed portion after exposure. The reason for this has not yet been determined, but the inventors speculate as follows.

[0056] That is, in the exposure process of manufacturing multilayer printed circuit boards, compound (A) does not have functional groups that participate in the photocuring reaction during the exposure process, and therefore does not hinder the photocuring reaction. In addition, compound (A) does not have a framework that hinders light transmittance, and also has very excellent light transmittance. Therefore, even if compound (B) is included along with compound (A), photopolymerization will still occur, and a cured product can be appropriately obtained.

[0057] Furthermore, compound (A) does not participate in the photocuring reaction, and therefore can exist in the resin composition of the unexposed portion. Thus, during the developing process, if the alkaline developer flows into the unexposed portion, the alkaline component in the alkaline developer and the carboxyl group in compound (A) can suitably form a salt. This increases the water solubility of the unexposed portion, so even if the unexposed portion contains photocuring components such as maleimide compound (C) and photocuring initiator (D), these components can be encapsulated and dissolved together with them in the alkaline developer. On the other hand, since compound (A) is mixed with the photocuring components in the composition, when only compound (A) is present, areas where the alkaline developer cannot penetrate are locally formed between compound (A) and these components, resulting in areas of low solubility. As a result, when only compound (A) is present, dissolution residues are formed in the unexposed portion, and a high-precision resist pattern cannot be obtained. However, the resin composition of this embodiment contains compound (A) and also compound (B) containing one or more carboxyl groups. It can be inferred that because compound (B) has a different structure from compound (A), it can be mixed with the components involved in photocuring in the composition, unlike compound (A). Furthermore, because compound (B) has one or more carboxyl groups, it is easier for the alkaline developer to flow into it. Therefore, areas in the unexposed areas where the alkaline developer cannot penetrate are less likely to form, increasing its solubility in the alkaline developer and thus imparting superior alkaline developability. Additionally, it can be inferred that because compound (B) has one or more carboxyl groups, by including compound (B), it is easier to form salts with the alkaline components in the alkaline developer in the unexposed areas, thus also imparting superior alkaline developability.

[0058] A solution of N-methylpyrrolidone containing 1% by mass of compound (A) was prepared. When the transmittance of the solution was measured using active energy X-rays containing a wavelength of 365 nm (i-rays), the transmittance was 5% or more. This compound (A) exhibits very excellent light transmittance. Furthermore, when the transmittance of the solution was measured using active energy X-rays containing a wavelength of 405 nm (h-rays), the transmittance was 5% or more. Excellent light transmittance was also observed under these conditions. When using this compound (A), for example, when manufacturing printed circuit boards with high-density and high-fine wiring formation (patterning) using direct drawing exposure, the photoradical reaction of maleimide occurs effectively even when using active energy X-rays containing a wavelength of 405 nm (h-rays). From the perspective of obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 365 nm (i-rays) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. From the perspective of obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 405 nm (h-rays) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. It should be noted that the upper limits for the transmittance at a wavelength of 365 nm (i-rays) and the transmittance at a wavelength of 405 nm (h-rays) are, for example, 99.9% or less.

[0059] In compound (A), in formula (1), R1 independently represents a group or hydrogen atom represented by formula (2). From the perspective of imparting superior alkali developability, R1 preferably contains two or more groups represented by formula (2), more preferably three or more, and even more preferably all R1 are groups represented by formula (2). If the carbonyl group in formula (2) is positioned at position 1 relative to the cyclohexane ring, and a carboxyl group is bonded at position 2 relative to that carbonyl group, then the other carboxyl group can be bonded to any one of positions 3 to 6 of the cyclohexane ring. Furthermore, in the group represented by formula (2), the structure of the carbonyl group bonded to the cyclohexane ring and the two carboxyl groups has a stereostructure; therefore, compound (A) exists in the form of cis, trans, and a mixture of cis and trans isomers. That is, compound (A) can be a single isomer, or a mixture containing two or more isomers.

[0060] In formula (1), regarding R1, from the perspective of imparting superior alkaline developability, it is preferable that at least one R1 is a group shown in formula (3). That is, in the group shown in formula (3), the stereostructure of the carbonyl group at position 1 and the carboxyl group at position 2 of the cyclohexane ring is preferably cis-form. Regarding the other carboxyl group, its stereostructure can be cis-form or trans-form. From the perspective of imparting further superior alkaline developability, R1 preferably contains two or more groups shown in formula (3), more preferably three or more, and even more preferably all R1 are groups shown in formula (3). If at least one R1 is a group shown in formula (3), the present inventors speculate that it can impart superior alkaline developability, although this has not yet been determined. That is, if the carbonyl group at position 1 and the carboxyl group at position 2 are cis-form, then in the resin composition, the carboxyl group at position 2 can more easily form a salt stereostructure with the alkaline component in the alkaline developer. Furthermore, it exhibits a stereostructure that is also readily compatible with the carboxyl group in compound (B) described later. Therefore, it can be inferred that this is because the water solubility is further enhanced, further promoting the inflow of the alkaline developer into the resin composition.

[0061]

[0062] In equation (3), -* represents the atomic bond that connects to the oxygen atom (O) directly connected to R1 in equation (1).

[0063] R2 independently represents a hydrogen atom, or a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms.

[0064] Examples of straight-chain or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl.

[0065] From the viewpoint of exhibiting better solubility in solvents, R2 is preferably a straight-chain alkyl group having 1 to 6 carbon atoms, more preferably methyl, ethyl, n-propyl, 2-butyl, isobutyl, tert-butyl, and n-pentyl, and even more preferably methyl, ethyl, and n-propyl.

[0066] From the viewpoint of being able to impart better alkaline developability and thus exhibit better solubility in solvents, compound (A) is preferably the compound shown in formula (5) and the compound shown in formula (6), and more preferably the compound shown in formula (5).

[0067]

[0068] In the resin composition, from the perspective of imparting better alkali developability and enabling the resin composition to exhibit better curability without hindering the photocuring reaction, the content of compound (A) is preferably 10 to 99 parts by mass relative to 100 parts by mass of the total of compound (A) and compound (B), more preferably 20 to 98 parts by mass, further preferably 30 to 97 parts by mass, and even more preferably 35 to 96 parts by mass.

[0069] In the resin composition, from the perspective of imparting better alkali developability and enabling the resin composition to exhibit better curability without hindering the photocuring reaction, the content of compound (A) relative to 100 parts by weight of the resin solids in the resin composition is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, further preferably 1.0 to 15 parts by weight, even more preferably 1.5 to 10 parts by weight, and even more preferably 2.0 to 10 parts by weight.

[0070] In the resin composition, when it contains the following compounds (B), as well as the following maleimide compound (C) and the following photocuring initiator (D), from the viewpoint of imparting better alkali developability and enabling the resin composition to exhibit better curability without hindering the photocuring reaction, the content of compound (A) is preferably 0.1 to 20 parts by mass relative to the total of 100 parts by mass of compound (A), compound (B), maleimide compound (C) and photocuring initiator (D), more preferably 0.5 to 15 parts by mass, further preferably 1.0 to 10 parts by mass, and even more preferably 2.0 to 9.0 parts by mass.

[0071] [Method for manufacturing compound (A)]

[0072] Compound (A) can be manufactured by known methods, for example by a process involving esterification of the alcohol compound of formula (7) with the anhydride (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride) of formula (8). It should be noted that, due to the stereostructure of the two carbonyl groups and one carboxyl group bonded to the cyclohexane ring, the anhydride of formula (8) exists in cis, trans, and mixtures of cis and trans isomers. That is, the anhydride of formula (8) can be a single isomer, or a mixture containing two or more isomers.

[0073]

[0074] In formula (7), R6 independently represents a hydrogen atom or a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms.

[0075] As a straight-chain alkyl or branched alkyl with 1 to 6 carbon atoms, including its preferred form, R2 in the aforementioned formula (1) can be referred to.

[0076]

[0077] Examples of alcohol compounds represented by formula (7) include, for example, bis(trimethylolethane), bis(trimethylolpropane), bis(trimethylolbutane), bis(trimethylolpentane), 2,2'-(oxybis(methylene))bis(propane-1,3-diol), 2,2'-(oxybis(methylene))bis(2-methylpropane-1,3-diol) and 2-((2,2-bis(hydroxymethyl)butoxy)methyl)-2-methylpropane-1,3-diol.

[0078] As the anhydride represented by formula (8), from the viewpoint of imparting better alkaline developability when using compound (A) to manufacture the cured product, it is preferable to include the anhydride represented by formula (9) (cis-,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride). That is, in the anhydride represented by formula (9), when the carbonyl group is positioned at positions 1 and 2 relative to the cyclohexane ring, the stereostructure of the carbonyl group bonded to position 4 relative to the carbonyl group and the two carbonyl groups is preferably cis-form.

[0079]

[0080] Esterification can be carried out in a solvent or under solvent-free conditions. There are no particular limitations on the solvent, as long as it does not react with alcohols or acid anhydrides.

[0081] Examples of such solvents include halogenated solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosol solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0082] Among them, from the viewpoint of being able to more fully dissolve alcohol compounds and acid anhydrides, halogenated solvents, aprotic polar solvents, ketone solvents, and ester solvents are preferred.

[0083] Dichloromethane is preferred as a halogen-containing solvent. Dimethylacetamide is preferred as an aprotic polar solvent. Methyl ethyl ketone is preferred as a ketone solvent. Propylene glycol monomethyl ether is preferred as a cellosol solvent. Butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred as ester solvents.

[0084] When using solvent, the amount used is typically 20 to 2000 parts by mass relative to the total 100 parts by mass of the alcohol and acid anhydride.

[0085] Esterification can occur without a catalyst or with a catalyst.

[0086] When a catalyst is used, examples of catalysts include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trichloroacetic acid, and trifluoroacetic acid; metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; amine compounds such as triethylamine, tripropylamine, diisopropylethylamine, and tributylamine; aliphatic amines with aromatic rings such as aniline, N-methylaniline, N,N-dimethylaniline, and benzylamine; and pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, etc. Heterocyclic compounds such as azoles, triazoles, and tetraazoles; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, and trioctylmethylammonium acetate; orthotitanic acids such as tetraethyl orthotitanic acid and tetramethyl orthotitanic acid; and metal soaps such as tin octoate, cobalt octoate, zinc octoate, manganese octoate, calcium octoate, sodium octoate, and potassium octoate. These catalysts can be used alone or in appropriate mixtures of two or more. From the viewpoint of better reactivity, amine compounds, aliphatic amines with aromatic rings, and heterocyclic compounds are preferred, with triethylamine and 4-dimethylaminopyridine being more preferred. Furthermore, the amount of catalyst used is typically 0.0001 to 1000 parts by mass relative to 1 part by mass of the alcohol compound.

[0087] Regarding methods of adding catalysts, examples include: adding them directly to alcohol compounds and / or acid anhydrides; and adding a solution of the catalyst, which is dissolved in a soluble solvent, to alcohol compounds, acid anhydrides, and / or solvents containing them.

[0088] When esterification is carried out using a catalyst, the reaction temperature is not particularly limited by the amount of catalyst or the solvent used, and is typically -20 to 150°C. Furthermore, the reaction time is not particularly limited, and is typically 0.5 to 100 hours. The reaction can be completed in one stage or in two or more stages.

[0089] In this embodiment, the alcohol compound represented by formula (7) and the acid anhydride represented by formula (8) are relatively highly reactive, and therefore esterification can occur even without a catalyst. As the acid anhydride represented by formula (8), it is preferable to include the acid anhydride represented by formula (9) to enhance its reactivity with the alcohol compound. In this specification, "without a catalyst" means that no catalyst is added or only a very small amount is added to facilitate the esterification reaction. Specifically, this means that in the reaction, the catalyst content is 50 ppm or less relative to 1 part by mass of the alcohol compound represented by formula (7). Furthermore, the catalyst content that facilitates the esterification reaction is preferably 0 ppm.

[0090] When esterification is carried out under catalyst-free conditions, halogenated solvents, ketone solvents, and ester solvents are preferred as solvents from the viewpoint of being able to fully dissolve the alcohol compound and acid anhydride, and also to dissolve the resulting compound (A) more fully. Furthermore, halogenated solvents and ester solvents are more preferred from the viewpoint of exhibiting better solubility and further suppressing the hydrolysis of acid anhydride. Moreover, ester solvents are further preferred from the viewpoint of enabling the alcohol compound to react better with the acid anhydride, further suppressing the hydrolysis of acid anhydride, and reducing environmental impact. As a halogenated solvent, dichloromethane is preferred from the viewpoint of exhibiting better solubility. As a ketone solvent, methyl ethyl ketone is preferred from the viewpoint of exhibiting better solubility. As an ester solvent, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred from the viewpoint of exhibiting better solubility.

[0091] By using this solvent under catalyst-free conditions, the steps of separating compound (A) from the reaction mixture described later, as well as the purification steps, can be eliminated. It should be noted that the reaction temperature and reaction time are as described below.

[0092] The rationale for this is not yet certain, but the inventors speculate as follows: By using halogen-containing solvents, ketone solvents, and ester solvents, the hydrolysis of the acid anhydride shown in formula (8) can be more appropriately suppressed, further suppressing side reactions other than the target esterification reaction. Therefore, it is speculated that impurities are less likely to be generated, and the target product with high purity can be obtained.

[0093] In addition, regarding the amount of solvent used, it is usually 20 to 2000 parts by mass relative to the total 100 parts by mass of alcohol compound and acid anhydride. From the perspective of further reducing the environmental impact, it is preferably 20 to 1000 parts by mass, and more preferably 20 to 500 parts by mass.

[0094] When esterification is carried out without a catalyst, the reaction temperature of esterification can be appropriately set according to the solvent used, typically from -20 to 150°C, and more preferably from 0 to 150°C, and even more preferably from 20 to 120°C, for better esterification.

[0095] When esterification is carried out without a catalyst, the reaction time is typically 0.5 to 100 hours. From the perspective of suppressing side reactions and ensuring better esterification, a reaction time of 0.5 to 80 hours, and even more preferably 0.5 to 50 hours, is preferred. It should be noted that the reaction can be completed in one stage or in two or more stages.

[0096] When using an ester solvent, the alcohol compound can be more fully esterified with the acid anhydride under catalyst-free conditions. This reduces the cost of catalysts, eliminates the need for catalyst removal, minimizes impurities, and yields compounds of relatively high purity. Therefore, these manufacturing conditions also eliminate the need for separating compound (A) from the reaction mixture (described later) and for purification. It should be noted that the reaction temperature and reaction time are as described above.

[0097] The rationale for this is still uncertain, but the inventors speculate as follows: The ester solvent can further suppress the hydrolysis of the anhydride shown in formula (8), and can further suppress side reactions other than the target esterification reaction. Therefore, it is speculated that impurities are less likely to form compared to other solvents, resulting in a higher purity target product.

[0098] Regarding methods for separating compound (A) as the target compound from a reaction mixture containing compound (A), if the target compound precipitates from the reaction solvent, separation can be achieved by filtration or centrifugation. Alternatively, if the target compound is dissolved in the reaction solvent, precipitation can be achieved by distilling off the solvent under reduced pressure, adding a suitable unsuitable solvent to the reaction mixture, or discharging the reaction mixture into an unsuitable solvent, followed by filtration or centrifugation. It should be noted that unsuitable solvents include hydrocarbons such as hexane, heptane, cyclohexane, toluene, and xylene. One of these solvents can be used alone, or two or more can be used in appropriate combinations.

[0099] If further purification of the isolated compound (A) is required, it can be performed using known methods. Examples of such methods include distillation, recrystallization, column chromatography, sludge treatment, and activated carbon treatment.

[0100] The obtained compound (A) can be identified by known methods such as NMR (nuclear magnetic resonance analysis). The purity of compound (A) can be analyzed by methods such as GPC, liquid chromatography, and IR spectroscopy. Volatile components such as byproducts and residual solvents in compound (A) can be quantitatively analyzed by methods such as GPC and gas chromatography. Residual halides in compound (A) can be identified by methods such as liquid chromatography-mass spectrometry, or quantitatively determined by ion chromatography after potentiometric titration with silver nitrate solution or decomposition based on combustion.

[0101] [Compound (B)]

[0102] The resin composition of this embodiment includes a compound (B) containing one or more carboxyl groups, other than compound (A) shown in formula (1). Compound (B) is not particularly limited as long as it contains one or more carboxyl groups. The carboxyl group can be a salt such as a sodium salt or a potassium salt, and if it contains two or more carboxyl groups, it can be an anhydride formed by their linkage. Furthermore, the molecule of compound (B) may contain functional groups such as epoxy groups or (meth)acryloyl groups. Compound (B) can be used alone or in combination with two or more compounds.

[0103] In this embodiment, during the exposure process of manufacturing a multilayer printed circuit board, by using a resin composition that contains both compound (A) and compound (B), a cured product can be obtained more effectively without hindering the photocuring reaction. Furthermore, during the development process, a resin composition containing both compound (A) and compound (B) can be obtained, which imparts superior alkaline developability to the unexposed portions of the resin composition after exposure.

[0104] When preparing an N-methylpyrrolidone solution containing 1% by mass of compound (B), and measuring its transmittance using active energy rays containing a wavelength of 365 nm (i-rays), the transmittance is preferably 5% or more. This compound (B) exhibits very excellent light transmittance. Furthermore, when measuring the transmittance of the N-methylpyrrolidone solution containing 1% by mass of compound (B) using active energy rays containing a wavelength of 405 nm (h-rays), the transmittance is preferably 5% or more, which also exhibits very excellent light transmittance. When using this compound (B), even when using active energy rays containing a wavelength of 405 nm (h-rays) to manufacture printed circuit boards with high-density and high-fine wiring formation (patterns), for example, maleimide photoradical reactions occur effectively. From the perspective of obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 365 nm (i-rays) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. From the perspective of obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 405 nm (h-rays) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. It should be noted that the upper limits for the transmittance at a wavelength of 365 nm (i-rays) and the transmittance at a wavelength of 405 nm (h-rays) are, for example, 99.9% or less, and can be 100% or less.

[0105] In this embodiment, from the perspective of obtaining better alkaline developability, the molecule of compound (B) preferably contains 1 to 10 carboxyl groups, and more preferably contains an average of 2 to 4 carboxyl groups.

[0106] From the viewpoint of further improving developability, the molecular weight of compound (B) is preferably 50 to 10,000, more preferably 100 to 8,000, even more preferably 130 to 6,000, and even more preferably 150 to 5,000.

[0107] From the viewpoint of further improving developability, the mass-average molecular weight of compound (B) is preferably 50 to 10,000, more preferably 100 to 8,000, and even more preferably 150 to 5,000.

[0108] Examples of compounds (B) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, heteroatom compounds containing one or more carboxyl groups, and acid anhydrides. These compounds (B) may be used alone or in appropriate combinations of two or more.

[0109] (Aliphatic compounds containing one or more carboxyl groups)

[0110] Examples of aliphatic compounds containing one or more carboxyl groups include chain-like aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, chain-like aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may contain hydrogen atoms and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups within the molecule. Furthermore, when these compounds contain two or more carboxyl groups within the molecule, they can be acid anhydrides formed by their interconnection. When these compounds contain carboxylalkyl groups within the molecule, they can be acid anhydrides formed by the interconnection of carboxylalkyl and carboxyl groups. When these compounds contain two or more carboxylalkyl groups within the molecule, they can be acid anhydrides formed by their interconnection.

[0111] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0112] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexyloxy, and 2-methylpropoxy.

[0113] Examples of aryloxy groups include phenoxy and p-tolyloxy.

[0114] Examples of aryl groups include phenyl, tolyl, benzyl, methylbenzyl, xylyl, mesitylene, naphthyl, and anthracene.

[0115] Examples of aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl.

[0116] Examples of carboxyl alkyl groups include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl.

[0117] Examples of chain-like aliphatic monocarboxylic acids include saturated fatty acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, hexanoic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid, unsaturated fatty acids such as oleic acid, transoleic acid, erucic acid, nervonic acid, linolenic acid, linolenic acid, eicosapentaenoic acid, linoleic acid and linolenic acid, as well as chain-like aliphatic monocarboxylic acids whose molecules contain one or more groups shown in formula (11).

[0118] Examples of alicyclic monocarboxylic acids include monocyclic carboxylic acids such as cyclopropane carboxylic acid, cyclopropene carboxylic acid, cyclobutane carboxylic acid, cyclobutene carboxylic acid, cyclopentane carboxylic acid, cyclopentene carboxylic acid, cyclohexane carboxylic acid, cyclohexene carboxylic acid, cycloheptane carboxylic acid, cycloheptene carboxylic acid, cyclooctane carboxylic acid and cyclooctene carboxylic acid, polycyclic or bridged alicyclic carboxylic acids such as norbornene carboxylic acid, tricyclic decane carboxylic acid, tetracyclic dodecane carboxylic acid, adamantane carboxylic acid, methyl adamantane carboxylic acid, ethyl adamantane carboxylic acid and butyl adamantane carboxylic acid, and alicyclic monocarboxylic acids containing one or more groups shown in formula (11) in their molecules.

[0119] As chain-like aliphatic polycarboxylic acids, examples include carboxylic acids obtained by further adding one or more carboxyl groups to chain-like aliphatic monocarboxylic acids. Examples include malonic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid, as well as chain-like aliphatic polycarboxylic acids whose molecules contain one or more groups represented by formula (11).

[0120] As alicyclic polycarboxylic acids, examples include carboxylic acids obtained by adding one or more carboxyl groups to an alicyclic monocarboxylic acid. Examples of examples include monocyclic carboxylic acids such as cyclopropane dicarboxylic acid, cyclopropane dicarboxylic acid, cyclopropane tricarboxylic acid, cyclopropane tricarboxylic acid, cyclobutane dicarboxylic acid, cyclobutene dicarboxylic acid, cyclobutane tricarboxylic acid, cyclobutene tricarboxylic acid, cyclobutane tetracarboxylic acid, cyclobutene tetracarboxylic acid, cyclopentane dicarboxylic acid, cyclopentene dicarboxylic acid, cyclopentane tricarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentene tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, cyclohexene tricarboxylic acid, cyclohexane tetracarboxylic acid, cyclohexene tetracarboxylic acid, cyclohexane pentacarboxylic acid, cyclohexene pentacarboxylic acid, cyclohexane hexacarboxylic acid, cyclohexene hexacarboxylic acid, cycloheptane dicarboxylic acid, cycloheptene dicarboxylic acid, cyclooctane dicarboxylic acid, and cyclooctene dicarboxylic acid; polycyclic or bridged alicyclic dicarboxylic acids such as norbornane dicarboxylic acid and adamantane dicarboxylic acid; and alicyclic polycarboxylic acids containing one or more groups shown in formula (11) in their molecules.

[0121] (Aromatic compounds containing one or more carboxyl groups)

[0122] Examples of parent skeletons for aromatic compounds containing one or more carboxyl groups include benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphtholic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, and anthracene pentacarboxylic acid. Aromatic compounds may have, for example, hydrogen atoms and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups on the aromatic ring of these parent skeletons. Furthermore, when these compounds have two or more carboxyl groups within their molecule, they can be anhydrides formed by their interconnection. When these compounds have carboxylalkyl groups within their molecule, they can be anhydrides formed by the interconnection of carboxylalkyl and carboxyl groups. When these compounds have two or more carboxylalkyl groups within their molecule, they can be anhydrides formed by their interconnection. For these substituents, refer to the foregoing. In addition, as aromatic compounds containing one or more carboxyl groups, examples of aromatic compounds whose molecules contain one or more groups shown in formula (11) and one or more carboxyl groups can also be listed.

[0123] (Heteroatom compounds containing one or more carboxyl groups)

[0124] Examples of heteroatom compounds containing one or more carboxyl groups as parent skeletons include compounds containing one or more carboxyl groups on heterocycles such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinine ring, chromene, thiathracene, phenothiazine, phenoxazine, oxanthracene, acridine, phenothiazine, and carbazole. These heteroatom compounds may have substituents such as hydrogen atoms, alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups on these parent skeletons. Furthermore, when these compounds have two or more carboxyl groups within their molecule, they can be anhydrides formed by their interconnection. When these compounds have carboxylalkyl groups within their molecule, they can be anhydrides formed by the interconnection of carboxylalkyl and carboxyl groups. When these compounds have two or more carboxylalkyl groups within their molecule, they can be anhydrides formed by their interconnection. For these substituents, refer to the foregoing. In addition, as heteroatom compounds containing one or more carboxyl groups, examples can also be listed that contain one or more groups shown in formula (11) and one or more carboxyl groups in their molecules.

[0125] As compound (B), from the perspective of the unexposed portion being more prone to collapse and the alkaline developer flowing more easily, and being able to impart better alkaline developability to the resin composition, it is preferably selected from at least one of the group consisting of a fully hydrogenated aromatic polycarboxylic acid, an anhydride of a partially hydrogenated aromatic polycarboxylic acid, and an acid-modified epoxy (meth)acrylate.

[0126] Anhydrides of aromatic polycarboxylic acids, both complete and partial hydrides, include, for example, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride; 1,2,3-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, 3,3 Anhydrides of the fully hydrogenated or partially hydrogenated forms of ',4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxobisphthalic acid, diphenylmethanetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, anthracenetetracarboxylic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, phenylpentacarboxylic acid, and phenylhexacarboxylic acid.

[0127] From the viewpoint that the unexposed section is more prone to collapse and that alkaline developer is more likely to flow in, thus imparting superior alkaline developability to the resin composition, the anhydrides of fully hydrogenated aromatic polycarboxylic acids and the anhydrides of partially hydrogenated aromatic polycarboxylic acids preferably have alicyclic structures such as monocyclic cycloalkanes like cyclopentane and cyclohexane; monocyclic cycloolefins like cyclopropene and cyclohexene; bicyclic alkanes like bicyclic undecane and decahydronaphthalene; and bicyclic alkenes like norbornene and norbornadiene. More preferably, they have monocyclic cycloalkanes or monocyclic cycloolefins. Examples of such preferred anhydrides include, for instance, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride. From the viewpoint that the unexposed portion is more prone to collapse and the alkaline developer is more prone to flow in, thereby imparting more excellent alkaline developability to the resin composition, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is preferred, and cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is even more preferred.

[0128] As an acid-modified epoxy (meth)acrylate, a compound obtained by reacting an epoxy resin (i), at least one compound selected from the group consisting of acrylic acid and methacrylic acid (ii), and at least one compound selected from the group consisting of a carboxylic acid compound and an anhydride containing a carboxylic acid compound (iii) can be listed. As such an acid-modified epoxy (meth)acrylate, a chain aliphatic monocarboxylic acid containing one or more groups shown in formula (11), an alicyclic monocarboxylic acid containing one or more groups shown in formula (11), a chain aliphatic polycarboxylic acid containing one or more groups shown in formula (11), and an alicyclic polycarboxylic acid containing one or more groups shown in formula (11) can be listed. As an aromatic compound containing one or more carboxyl groups, an aromatic compound containing one or more groups shown in formula (11) and one or more carboxyl groups can be listed. In addition, as a heteroatom compound containing one or more carboxyl groups, a heteroatom compound containing one or more groups shown in formula (11) and one or more carboxyl groups can be listed.

[0129] As an acid-modified epoxy (meth)acrylate, from the perspective that the unexposed portion is more prone to collapse and that the alkaline developer is more likely to flow in, and that it can impart better alkaline developability to the resin composition, it is preferred to be a compound containing one or more groups shown in formula (10) and one or more groups shown in formula (11) in its molecule.

[0130]

[0131] In equation (10), -* represents an atomic bond.

[0132]

[0133] In formula (11), -* represents an atomic bond, and R7 represents a hydrogen atom, or a straight-chain alkyl or branched alkyl with 1 to 6 carbon atoms.

[0134] Examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl. As R7, from the viewpoint of further improving the reactivity of photocuring, a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms is preferred; more preferably, a hydrogen atom, methyl, ethyl, n-propyl, 2-butyl, isobutyl, tert-butyl, and n-pentyl are preferred; and even more preferably, a hydrogen atom, methyl, ethyl, and n-propyl are preferred.

[0135] As an acid-modified epoxy (meth)acrylate, the compound shown in formula (12) is further preferred from the aspects that the unexposed part is more likely to collapse as a whole, the alkaline developer is more likely to flow in, and the resin composition can be given more excellent alkaline developability.

[0136]

[0137] In formula (12), each of R8 independently represents a hydrogen atom or a methyl group. From the viewpoint of further improving the reactivity of the photocuring reaction, it is preferable to include hydrogen atoms, and more preferably all of R8 are hydrogen atoms.

[0138] R9 can independently represent a hydrogen atom or an optional hydrocarbon group with 1 to 22 carbon atoms having substituents.

[0139] Examples of hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups with 1 to 22 carbon atoms, preferably 1 to 14, and more preferably 1 to 10; alicyclic hydrocarbon groups with 3 to 22 carbon atoms, preferably 3 to 14, and more preferably 3 to 10; and aromatic hydrocarbon groups with 6 to 22 carbon atoms, preferably 6 to 14, and more preferably 6 to 10.

[0140] Examples of aliphatic hydrocarbon groups include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, 1,1-dimethylbutyl, and 1,1,3-trimethylbutyl; straight-chain or branched alkenyl groups such as vinyl, allyl, and isopropenyl; and straight-chain or branched alkyne groups such as ethynyl and propynyl.

[0141] Examples of alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methyl-1-cyclohexyl, and adamantyl alkyl cyclic saturated hydrocarbon groups; and cyclopentadienyl, indene, and fluorenyl cyclic unsaturated hydrocarbon groups.

[0142] Examples of aromatic hydrocarbon groups include non-substituted aryl groups such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracene; and alkyl-substituted aryl groups such as tolyl, dimethylphenyl, isopropylphenyl, tert-butylphenyl, and di-tert-butylphenyl.

[0143] These hydrocarbon groups may optionally have at least one hydrogen atom replaced by another hydrocarbon group. Examples of hydrocarbon groups in which at least one hydrogen atom is replaced by another hydrocarbon group include aryl-substituted alkyl groups such as benzyl and cumyl; and cyclic saturated hydrocarbon-substituted alkyl groups such as cyclohexylmethyl.

[0144] The hydrocarbon group having 1 to 22 carbon atoms as an optional substituent is preferably a straight-chain alkyl group or a branched-chain alkyl group.

[0145] From the viewpoint of further improving the heat resistance of the cured product, R9 preferably contains methyl groups, and more preferably R9 is entirely composed of methyl groups.

[0146] R 10 Each group represents independently the group shown in formula (10), the group shown in formula (11), or a hydroxyl group. From the viewpoint of further improving peelability after development, the inclusion of a hydroxyl group is preferred. Additionally, the use of groups containing R... 10 Compounds containing the group shown in formula (10) are also preferred from the viewpoint of further improving developability. Using compounds containing R... 10 Compounds with the group shown in formula (11) are also preferred from the viewpoint of further improving the reactivity of photocuring. In formula (11), R7 represents a hydrogen atom or a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms. Among these, from the viewpoint of further improving the reactivity of the photocuring reaction, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

[0147] From the viewpoint of further improving developability, the acid value of the compound shown in formula (12) is preferably 30 mg KOH / g or more, and from the viewpoint of further improving developability, it is more preferably 50 mg KOH / g or more. Furthermore, from the viewpoint of further preventing dissolution by the developer after curing with active energy rays, the acid value of the compound is preferably 120 mg KOH / g or less, and from the viewpoint of further preventing dissolution, it is more preferably 110 mg KOH / g or less. It should be noted that in this specification, "acid value" refers to the value measured by the method based on JIS K0070:1992.

[0148] As the compound represented by formula (12), from the viewpoint of further improving the reactivity of the photocuring reaction, the heat resistance of the cured product, the peelability and developability after development, it is preferable to contain any one or more of compounds (A1) to (A5), more preferably to contain at least compound (A1), even more preferably to contain any two or more of compounds (A1) to (A5), and even more preferably to contain compound (A1) and contain any one or more of compounds (A2) to (A5). As the compound represented by formula (12), it is also preferable to contain at least compounds (A2) and (A3).

[0149]

[0150]

[0151] As shown in formula (12), commercially available products can also be used. Examples include KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H, and KAYARAD (registered trademark) ZCR-601H (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.).

[0152] In the resin composition, from the perspective that the unexposed portion is more prone to collapse and the alkaline developer is more likely to flow in, and that the resin composition can be given better alkaline developability, the content of compound (B) is preferably 1.0 to 90 parts by mass relative to 100 parts by mass of the total of compound (A) and compound (B), more preferably 2.0 to 80 parts by mass, further preferably 3.0 to 70 parts by mass, and even more preferably 4.0 to 65 parts by mass.

[0153] In the resin composition, from the perspective that the unexposed portion is more prone to collapse and the alkaline developer is more prone to flow in, and that the resin composition can be given better alkaline developability, the content of compound (B) is preferably 0.05 to 30 parts by mass relative to 100 parts by mass of the resin solids in the resin composition, more preferably 0.1 to 20 parts by mass, further preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass.

[0154] In the resin composition, when compound (A) is included along with maleimide compound (C) and photocuring initiator (D), the content of compound (B) is preferably 0.05 to 30 parts by mass relative to the total of 100 parts by mass of compound (A), compound (B), maleimide compound (C) and photocuring initiator (D), more preferably 0.1 to 20 parts by mass, further preferably 0.2 to 15 parts by mass, and even more preferably 0.25 to 10 parts by mass.

[0155] [Maleimide compound (C)]

[0156] The resin composition of this embodiment preferably further comprises maleimide compound (C) (also referred to as component (C) or compound (C)).

[0157] As for the maleimide compound (C), there is no particular limitation as long as it is a compound having one or more maleimide groups in its molecule. Examples of such maleimide compounds (C) include, for example, bismaleimide (C1) described later, compounds shown in formula (15), compounds shown in formula (16), compounds shown in formula (17), compounds shown in formula (18), compounds shown in formula (19), compounds shown in formula (20), N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinephenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimide hexanoic acid, 4-maleimide butyric acid, bis(4-maleimidephenyl)methane, 2,2-bis... (4-(4-maleimidephenoxy)-phenyl)propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bisciconimide, m-phenylene bisciconimide, p-phenylene bisciconimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl 4,4-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecanane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 4,4-diphenyl ether bismaleimide Amines, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene, 4,4-diphenylmethane bisciconimide, 2,2-bis[4-(4-ciconimide phenoxy)phenyl]propane, bis(3,5-dimethyl-4-ciconimide phenyl)methane, bis(3-ethyl-5-methyl-4-ciconimide phenyl)methane, bis(3,5-diethyl-4-ciconimide phenyl)methane, polyphenylmethane maleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, as well as prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds (C) can be used alone or in appropriate mixtures of two or more.

[0158] As the maleimide compound (C), a compound with excellent light transmittance is preferred.

[0159] When a maleimide compound (C) is included in the resin composition, from the perspective of imparting superior alkali developability and enabling the resin composition to exhibit good curability without hindering the photocuring reaction, the total content of the maleimide compound (C) relative to 100 parts by weight of the resin solids in the resin composition is preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight, and even more preferably 30 to 100 parts by weight. The lower limit of the total content of the maleimide compound (C) relative to 100 parts by weight of the resin solids in the resin composition can be 60 parts by weight or more, 70 parts by weight or more, or 80 parts by weight or more.

[0160] When the resin composition contains compounds (A) and (B) as well as the photocuring initiator (D) (described later), the content of maleimide compound (C) relative to a total of 100 parts by mass of compounds (A), (B), (C), and (D) is preferably 30 to 97 parts by mass, more preferably 40 to 96 parts by mass, and even more preferably 50 to 95 parts by mass. The lower limit of the content of maleimide compound (C) relative to a total of 100 parts by mass of compounds (A), (B), (C), and (D) can be 60 parts by mass or more, 70 parts by mass or more, or 80 parts by mass or more.

[0161] As the maleimide compound (C), it is preferable to include bismaleimide (C1) from the aspects of being able to exhibit better curability, better solubility in solvents, low melting point and better low water absorption. It is also preferable to include at least one of the compounds selected from the group consisting of the compound shown in formula (15), the compound shown in formula (16), the compound shown in formula (17), the compound shown in formula (18), the compound shown in formula (19) and the compound shown in formula (20) while including bismaleimide (C1). As the maleimide compound (C), from the viewpoint that it can exhibit better curability, better heat resistance and thermal stability, better solubility in solvents, lower melting point and better low water absorption, and better compatibility with other resins, it is preferable to include at least one of the following compounds selected from the group consisting of the compound shown in formula (15), the compound shown in formula (16) and the compound shown in formula (17) while containing bismaleimide (C1), and more preferably, it is preferable to include at least one of the following compounds selected from the group consisting of the compound shown in formula (15) and the compound shown in formula (16) while containing bismaleimide (C1).

[0162] (Bismaleimide compound (C1))

[0163] From the perspective of exhibiting better curability, better solubility in solvents, lower melting point, and better low water absorption, the resin composition of this embodiment preferably further comprises a bismaleimide compound (C1) (also referred to as component (C1)). The bismaleimide compound (C1) comprises the structural unit shown in formula (4) and maleimide groups located at both ends of the molecular chain.

[0164]

[0165] In formula (4), R3 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. R4 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. R5 each independently represents a hydrogen atom, a straight-chain alkyl or branched alkyl with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. n1 each independently represents an integer from 1 to 10.

[0166] Typically, maleimide compounds are difficult to develop in alkaline environments due to their extremely low water solubility and lack of reactivity with the alkaline components in alkaline developers. However, the resin composition, by containing both compound (A) and compound (B) and a bismaleimide compound (C1), exhibits both excellent photocurability and very good alkaline developability. The reason for this is not yet determined, but the inventors speculate as follows.

[0167] That is, the resin composition includes compound (A) which imparts excellent alkaline developability to the resin composition without hindering the photocuring reaction, and compound (B) which suitably controls the water solubility of the unexposed portion and imparts alkaline developability. Furthermore, the bismaleimide compound (C1) has a relatively long-chain and flexible structure, and therefore does not have a structure that would interact with the alkaline components in the alkaline developer. Therefore, during the developing process, when the alkaline developer flows into the unexposed portion (resin composition), the alkaline components in the alkaline developer can rapidly and suitably form salts with the carboxyl groups in compounds (A) and (B) without being hindered by the bismaleimide compound (C1), thus improving water solubility. The bismaleimide compound (C1) can dissolve in the alkaline developer in such a way that it is incorporated into compounds (A) and (B) along with them as they dissolve in the alkaline developer. Therefore, it can be inferred that the resin composition has excellent alkaline developability.

[0168] Furthermore, the inventors speculate that the excellent photocurability of the resin composition is due to the following reasons, by including bismaleimide compound (C1) in addition to compound (A) and compound (B).

[0169] Typically, maleimide compounds have poor light transmittance. Therefore, if a resin composition contains maleimide compounds, light cannot sufficiently reach the photocuring initiator dispersed in the resin composition, making it difficult for the photocuring initiator to generate free radicals. Consequently, the photoradical reaction of maleimide compounds is usually difficult to carry out, and even if the free radical polymerization and dimerization reaction of maleimide monomers occurs, its reactivity is very low. However, bismaleimide compound (C1) has the structural unit shown in formula (4), namely the alicyclic skeleton, and therefore has excellent light transmittance. In addition, compound (A) also has excellent light transmittance. Therefore, light can sufficiently reach the photocuring initiator, effectively causing the photoradical reaction of maleimide. Various active energy rays (light rays) can be used to photocur compounds (A), (B), and bismaleimide compound (C1) together with maleimide compound (C) and the photocuring initiator (D) described later, which are mixed as needed.

[0170] A chloroform solution containing 1% by mass of a bismaleimide compound (C1) was prepared. When the transmittance of the chloroform solution containing 1% by mass of a bismaleimide compound (C1) was measured using active energy X-rays containing a wavelength of 365 nm (i-rays), the transmittance was 5% or more, exhibiting very excellent light transmittance. Furthermore, when the transmittance of the chloroform solution containing 1% by mass of a bismaleimide compound (C1) was measured using active energy X-rays containing a wavelength of 405 nm (h-rays), the transmittance was 5% or more, exhibiting very excellent light transmittance. Therefore, when manufacturing printed circuit boards with high-density and high-fine wiring formation (patterning) using methods such as direct drawing exposure, the photoradical reaction of maleimide occurs effectively even when using active energy X-rays containing a wavelength of 405 nm (h-rays). From the viewpoint of exhibiting even better light transmittance, the transmittance at a wavelength of 365 nm (i-rays) is preferably 8% or more, more preferably 10% or more. From the viewpoint of manufacturing printed circuit boards with higher density and finer wiring formation (patterning), the transmittance at a wavelength of 405 nm (h-rays) is preferably 8% or more, more preferably 10% or more. It should be noted that the upper limits of the transmittance at a wavelength of 365 nm (i-rays) and the transmittance at a wavelength of 405 nm (h-rays) are, for example, 99.9% or less.

[0171] Generally, photocurable initiators tend to have lower absorbance for longer wavelengths of light. For example, when using active energy rays containing a wavelength of 405 nm (h-rays), this wavelength is relatively long and cannot be absorbed by conventional photocurable initiators. Unless a photocurable initiator capable of appropriately absorbing this light and generating free radicals is used, polymerization cannot proceed. Therefore, as the photocurable initiator (D) described later, when measuring the absorbance of a chloroform solution containing 0.01% by mass of the photocurable initiator (D), it is preferable to use a photocurable initiator exhibiting very excellent absorbance with an absorbance of 0.1 or more relative to light with a wavelength of 405 nm (h-rays).

[0172] As described above, the bismaleimide compound (C1) has excellent light transmittance. Therefore, even when using active energy rays containing, for example, wavelengths of 365 nm or 405 nm, light can sufficiently reach the photocuring initiator, allowing for a suitable free radical reaction using free radicals generated by the photocuring initiator. Photocuring can also be performed in compositions containing a large amount of the bismaleimide compound (C1).

[0173] Furthermore, the resin composition exhibits excellent alkali developability and photocurability. Additionally, the resulting cured product demonstrates excellent heat resistance, insulation reliability, and thermal stability. Therefore, according to this embodiment, protective films and insulating layers in multilayer printed circuit boards and semiconductor devices can be suitably formed.

[0174] The bismaleimide compound (C1) is not particularly limited as long as it achieves the effects of the present invention. From the viewpoint of obtaining a suitable viscosity and suppressing the increase of viscosity of the varnish, the mass-average molecular weight is preferably 100 to 5000, more preferably 300 to 4500.

[0175] Next, the structure of the bismaleimide compound (C1) will be described.

[0176] In formula (4) of the bismaleimide compound (C1), R3 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms. From the viewpoint of obtaining a more suitable viscosity and further controlling the viscosity increase of the varnish, R3 is preferably a straight-chain alkylene or branched alkylene, and more preferably a straight-chain alkylene.

[0177] From the viewpoint of obtaining a more suitable viscosity and further controlling the viscosity increase of the varnish, the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12.

[0178] Examples of linear or branched alkylene compounds include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyl dodecylene, methyl undecylene, methyl tridecylene, methyl tetradecylene, and methyl pentadecylene.

[0179] From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, the number of carbon atoms in the subalkenyl group is preferably 2 to 14, more preferably 4 to 12.

[0180] Examples of straight-chain or branched alkenyl groups include vinylidene, 1-methylvinylidene, allylidene, propenylidene, isopropenylidene, 1-butenylidene, 2-butenylidene, 1-pentenylidene, 2-pentenylidene, isopentylidene, cyclopentenylidene, cyclohexenylidene, and dicyclopentadienylidene.

[0181] In formula (4), R4 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, a straight-chain or branched alkylene group is preferred as R4, and a straight-chain alkylene group is more preferred.

[0182] From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12.

[0183] As a linear or branched alkylene group, refer to R3 mentioned above.

[0184] From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, the number of carbon atoms in the subalkenyl group is preferably 2 to 14, more preferably 4 to 12.

[0185] As a linear or branched alkenyl group, refer to R3 mentioned above.

[0186] In formula (4), R3 and R4 can be the same or different. From the point of view that it is easier to synthesize bismaleimide compounds (C1), it is preferred that they are the same.

[0187] In formula (4), each of R5 independently represents a hydrogen atom, a straight-chain alkyl or branched alkyl group having 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl group having 2 to 16 carbon atoms. From the viewpoint of obtaining a more suitable viscosity and being able to further control the viscosity rise of the varnish, each of R5 is preferably a hydrogen atom, or a straight-chain alkyl or branched alkyl group having 1 to 16 carbon atoms, more preferably 1 to 5 of the R5 groups (R5) are straight-chain alkyl or branched alkyl groups having 1 to 16 carbon atoms, and the remaining group (R5) is a hydrogen atom, and even more preferably 1 to 3 of the R5 groups (R5) are straight-chain alkyl or branched alkyl groups having 1 to 16 carbon atoms, and the remaining group (R5) is a hydrogen atom.

[0188] From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, the number of carbon atoms of the alkyl group is preferably 2 to 14, more preferably 4 to 12.

[0189] Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpent-3-yl, and n-nonyl.

[0190] From the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be further suppressed, the number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 4 to 12.

[0191] Examples of alkenyl groups that can be straight-chain or branched include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl.

[0192] In equation (4), n1 independently represents integers from 1 to 10.

[0193] Bismaleimide compounds (C1) have maleimide groups at both ends of their molecular chain. "Both ends" refers to the two ends of the molecular chain of the bismaleimide compound (C1). In the case where, for example, the structural unit shown in formula (4) is located at the end of the molecular chain of the bismaleimide compound (C1), this means that the maleimide group is present at the end of the molecular chain of R3, or at the end of the molecular chain on the N atom of the maleimide ring, or at both ends. Bismaleimide compounds (C1) may also have maleimide groups at both ends of their molecular chain.

[0194] The maleimide group is represented by formula (13), where the N atom is bonded to the molecular chain of the bismaleimide compound (C1). Furthermore, the maleimide groups bonded to the bismaleimide compound (C1) can be all the same or different, but preferably the maleimide groups at both ends of the molecular chain are the same.

[0195]

[0196] In equation (13), R 11 Each can independently represent a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. From the viewpoint of more suitable photocuring, R... 11 Ideally, both should consist of hydrogen atoms.

[0197] From the viewpoint that the number of carbon atoms in the alkyl group is more suitable for photocuring, it is preferably 1 to 3, and more preferably 1 to 2.

[0198] As for straight-chain alkyl or branched alkyl, refer to R5 above.

[0199] Examples of such bismaleimide compounds (C1) include, for example, maleimide compounds represented by formula (14). They can be used alone or in appropriate combinations of two or more.

[0200]

[0201] In equation (14), a represents an integer from 1 to 10. From the viewpoint of obtaining a more suitable viscosity and further suppressing the increase in viscosity of the varnish, a is preferably an integer from 1 to 6.

[0202] Bismaleimide compounds (C1) can also be commercially available. Examples of commercially available products include MIZ-001 (trade name, maleimide compound containing formula (14)) manufactured by Nippon Kayaku Co., Ltd.

[0203] From the viewpoint that a cured product with a bismaleimide compound as the main component can be obtained in the resin composition, that photocurability can be further improved, and that better heat resistance and thermal stability can be obtained, the content of the bismaleimide compound (C1) in the resin composition preferably includes 10 to 90 parts by mass of 100 parts by mass of the resin solids component, more preferably 30 to 80 parts by mass, even more preferably 40 to 70 parts by mass, and even more preferably 45 to 65 parts by mass.

[0204] Furthermore, when the resin composition contains a bismaleimide compound (C1) and maleimide compounds other than bismaleimide compound (C1), from the viewpoint that a cured product with a bismaleimide compound as the main component can be obtained, that photocurability can be further improved, and that better heat resistance and thermal stability can be obtained, the content of the bismaleimide compound (C1) is preferably 10 to 90 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (C1) and maleimide compounds other than bismaleimide compound (C1), more preferably 30 to 80 parts by mass, even more preferably 40 to 70 parts by mass, and even more preferably 45 to 65 parts by mass. As a maleimide compound other than bismaleimide compound (C1), it is preferred to include at least one of the compounds selected from the group consisting of the compound shown in (15), the compound shown in (16), the compound shown in (17), the compound shown in (18), the compound shown in (19), and the compound shown in (20). More preferably, it includes at least one of the compounds selected from the group consisting of the compound shown in (15), the compound shown in (16), and the compound shown in (17). Even more preferably, it includes at least one of the compounds selected from the group consisting of the compound shown in (15) and the compound shown in (16).

[0205] Bismaleimide compounds (C1) can be used alone or in appropriate combinations of two or more.

[0206] (Method for manufacturing bismaleimide compound (C1))

[0207] Bismaleimide compound (C1) can be manufactured by known methods. For example, an addition polymerization reaction is carried out with 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a monomer containing a diamine such as a dimerizing diamine, and maleic anhydride at a temperature typically around 80–250°C, preferably around 100–200°C, for typically 0.5–50 hours, preferably 1–20 hours, to obtain an addition polymer. Subsequently, the addition polymer is subjected to an imidization reaction, i.e., a dehydration and ring-closing reaction, typically around 0.1–2 hours, preferably around 0.1–0.5 hours, at a temperature typically around 60–120°C, preferably around 80–100°C, thereby obtaining bismaleimide compound (C1).

[0208] Dimeric diamines are obtained, for example, by the reductive amination reaction of dimer acids. The amination reaction can be carried out by known methods, such as reduction using ammonia and a catalyst (e.g., the method described in Japanese Patent Application Publication No. 9-12712). Dimeric acids refer to dicarboxylic acids obtained by dimerization of unsaturated fatty acids through intermolecular polymerization reactions. While depending on the synthesis and purification conditions, they typically contain small amounts of monomeric acids, trimer acids, etc., in addition to dimer acids. The resulting molecule may retain intramolecular double bonds; however, in this embodiment, substances that reduce intramolecular double bonds to become saturated dicarboxylic acids through hydrogenation reactions are also included within the category of dimer acids. Dimeric acids are obtained by, for example, the polymerization of unsaturated fatty acids using Lewis acids and Brønsted acids as catalysts. Dimeric acids can be manufactured by known methods (e.g., the method described in Japanese Patent Application Publication No. 9-12712). Examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, transoleic acid, vaccenic acid, gadooleic acid, eicosapentaenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, tung oil acid, meadacid, dihyo-γ-linolenic acid, eicosatrienoic acid, stearidonicacid, arachidonic acid, eicosatetraenoic acid, adrenal acid, 5Z,8Z,10E,12E,14Z-eicosapentaenoic acid, osbond acid, clupatanodonic acid, docosahexaenoic acid, and nisinic acid. Unsaturated fatty acids typically have 4 to 24 carbon atoms, preferably 14 to 20.

[0209] In the manufacture of bismaleimide compounds (C1), it is preferable to first dissolve or disperse the diamine-containing monomer in an inert atmosphere such as argon or nitrogen in an organic solvent to form a slurry, thus preparing a monomer solution containing the diamine. Furthermore, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferably added to the aforementioned monomer solution containing the diamine after being dissolved or dispersed in an organic solvent to form a slurry, or in a solid state.

[0210] By adjusting the molar amounts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the total molar amounts of the monomer containing the diamine and the maleimide compound, any bismaleimide compound (C1) can be obtained.

[0211] In addition polymerization and imidization reactions, a variety of known solvents can be used. Examples of solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; and aliphatic alcohols with 1 to 10 carbon atoms such as methanol, ethanol, and propanol. Phenolic solvents containing aromatic groups, such as phenol and cresol; alcohols containing aromatic groups, such as benzyl alcohol; diols, such as ethylene glycol and propylene glycol, or diol ethers of these diols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of these diol ethers; cyclic ethers, such as dioxane and tetrahydrofuran; carbonates, such as ethylene carbonate and propylene carbonate; aliphatic hydrocarbons and aromatic hydrocarbons, such as toluene and xylene; and aprotic polar solvents, such as dimethyl sulfoxide. One of these solvents may be used alone or in combination of two or more, as needed.

[0212] Furthermore, a catalyst is preferably used in the imidization reaction. Examples of catalysts include tertiary amines and dehydration catalysts. Heterocyclic tertiary amines are preferred, such as pyridine, methylpyridine, quinoline, and isoquinoline. Examples of dehydration catalysts include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.

[0213] Regarding the amount of catalyst added, it is preferred that, for example, the imidizing agent is set to about 0.5 to 5.0 molar equivalents relative to the amide group, and the dehydration catalyst is set to 0.5 to 10.0 molar equivalents relative to the amide group.

[0214] After the imidization reaction is complete, the solution can be used as a solution of the bismaleimide compound (C1), or a poor solvent can be added to the reaction solvent to form the bismaleimide compound (C1) into a solid substance. Examples of poor solvents include water, methanol, ethanol, 2-propanol, ethylene glycol, triethylene glycol, 2-butanol, 2-pentanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol, and tert-butanol.

[0215] As mentioned above, maleimide compounds typically exhibit very low photoradical reactivity. However, as also mentioned above, bismaleimide compound (C1) possesses excellent light transmittance. Furthermore, compound (A) also exhibits excellent light transmittance. Therefore, by using bismaleimide compound (C1) in conjunction with compound (A), compound (B), maleimide compound (C) other than bismaleimide compound (C1) as needed, and photocuring initiator (D) as needed, light can sufficiently reach the photocuring initiator, effectively triggering the photoradical reaction of maleimide, thus enabling photocuring using various active energy rays.

[0216] Compound (A) and bismaleimide compound (C1) have excellent light transmittance. Therefore, even when using various active energy rays, especially active energy rays with a wavelength of 365 nm or 405 nm, the light will reach the photocuring initiator sufficiently to carry out a free radical reaction using the free radicals generated by the photocuring initiator. Photocuring can also be carried out in compositions containing maleimide compounds.

[0217] Furthermore, the resin composition exhibits excellent alkali developability and photocurability. In addition, the resulting cured product demonstrates excellent heat resistance, insulation reliability, and thermal stability, thus enabling the suitable formation of protective films and insulating layers.

[0218] Next, the compounds shown in formula (15) to those shown in formula (20) will be described.

[0219] (The compound shown in formula (15))

[0220] The compound represented by formula (15) is the following compound.

[0221]

[0222] In equation (15), R 12 R 13 and R 14 Each can independently represent a hydrogen atom, or optionally a straight-chain alkyl or branched alkyl group having 1 to 8 carbon atoms with substituents.

[0223] Examples of linear or branched alkyl groups having 1 to 8 carbon atoms and optionally containing substituents include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, and heptyl. The hydrogen atoms in these alkyl groups may optionally be substituted with halogen atoms such as fluorine and chlorine atoms, or with cyano groups. From the viewpoint of superior photocurability, heat resistance, and thermal stability, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, methyl, ethyl, isopropyl, and tert-butyl are preferred, more preferably methyl, ethyl, and isopropyl, and even more preferably methyl.

[0224] From the viewpoint of exhibiting superior photocurability, heat resistance and thermal stability, solubility in solvents, low melting point, low water absorption, and compatibility with other resins, the compound represented by formula (15) is even more preferred. The compound represented by formula (21) (also referred to as TMDM in this embodiment) is also preferred.

[0225]

[0226] (The compound shown in formula (16))

[0227] The compound represented by formula (16) is the following compound.

[0228]

[0229] In equation (16), R 15 R 16 and R 17 Each of the following can independently represent a hydrogen atom, a hydroxyl group, or a straight-chain or branched alkyl group with 1 to 6 carbon atoms that may have a substituent. n3 represents an integer from 1 to 10.

[0230] As a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms, R5 in the aforementioned formula (4) can be referred to. From the viewpoint of exhibiting better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, methyl, ethyl, n-propyl, and isopropyl are preferred as alkyl groups, and methyl is more preferred.

[0231] Additionally, R 15 R 16 and R 17 From the viewpoint of exhibiting superior solubility in solvents, R is preferred. 15 and R 17 It is a straight-chain alkyl or branched alkyl group having 1 to 6 carbon atoms, and R 16 It consists of hydrogen atoms. It should be noted that the preferred alkyl group is as described above.

[0232] From the viewpoint that it has better solubility in solvents, can obtain a more suitable viscosity, and can further control the increase of viscosity of the varnish, n3 is preferably an integer from 1 to 10, and more preferably an integer from 1 to 6.

[0233] As the compound shown in formula (16), commercially available products can be used, such as the compound shown in formula (22) (BCPH01 (trade name, Mw / Mn = 1.0 to 1.8) manufactured by Kunei Chemical Industry Co., Ltd., BCPH13 (trade name, Mw / Mn = 1.0 to 1.6) manufactured by Kunei Chemical Industry Co., Ltd.) and the compound shown in formula (23) (BMCX426 (trade name) manufactured by Kunei Chemical Industry Co., Ltd.).

[0234]

[0235] In equation (22), n 21 It is an integer from 1 to 5.

[0236]

[0237] In equation (23), n 22 It is an integer from 1 to 10.

[0238] (The compound shown in formula (17))

[0239] The compound shown in formula (17) is the following compound.

[0240]

[0241] In equation (17), R 18 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group; R 19 Each can be used independently to represent a hydrogen atom or a methyl group.

[0242] As R 18 From the viewpoint of exhibiting better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, methyl or ethyl resins are preferred.

[0243] As R 19 From the viewpoint of exhibiting better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, hydrogen atoms are preferred.

[0244] As the maleimide compound shown in formula (17), commercially available products can be used, such as BMI-70 (trade name) manufactured by KI Chemical Co., Ltd., as shown in formula (24).

[0245]

[0246] (The compound shown in formula (18))

[0247] The compound represented by formula (18) is the following compound.

[0248]

[0249] In equation (18), R 20 Each can independently represent a hydrogen atom or a methyl group. n4 represents an integer from 1 to 10.

[0250] As the maleimide compound shown in formula (18), commercially available products can be used, such as MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd., as shown in formula (25).

[0251]

[0252] In equation (25), n 31 It is an integer from 1 to 10.

[0253] (The compound shown in formula (19))

[0254] The compound represented by formula (19) is the following compound.

[0255]

[0256] In equation (19), R 21 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group.

[0257] As R 21 From the viewpoint of exhibiting better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, methyl or ethyl resins are preferred.

[0258] As the maleimide compound shown in formula (19), commercially available products can be used, such as BMI-80 (trade name) manufactured by KI Chemical Co., Ltd., as shown in formula (26).

[0259]

[0260] (The compound shown in formula (20))

[0261] The compound represented by formula (20) is the following compound.

[0262]

[0263] In equation (20), R 22 Each can independently represent a hydrogen atom or a methyl group. n5 represents an integer from 1 to 10.

[0264] As R 22 From the viewpoint of exhibiting better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, hydrogen atoms are preferred.

[0265] From the viewpoint that n5 has better solubility in solvents, can obtain a more suitable viscosity, and can further control the increase in viscosity of the varnish, it is more preferable to be an integer from 1 to 5.

[0266] As the maleimide compound shown in formula (20), commercially available products can be used, such as BMI-2300 (trade name) manufactured by Yamato Chemical Industries Co., Ltd., as shown in formula (27).

[0267]

[0268] In equation (27), n 41 It is an integer from 1 to 5.

[0269] In the resin composition, when at least one of the compounds selected from the group consisting of the compound shown in (15), the compound shown in (16), the compound shown in (17), the compound shown in (18), the compound shown in (19), and the compound shown in (20) is included as a maleimide compound, from the viewpoint of obtaining better heat resistance and thermal stability, the total content of these maleimide compounds is preferably 10 to 90 parts by mass of 100 parts by mass of resin solids in the resin composition, more preferably 20 to 70 parts by mass, further preferably 30 to 60 parts by mass, and even more preferably 35 to 55 parts by mass.

[0270] Furthermore, in the resin composition, when at least one of the compounds selected from the group consisting of the compound shown in (15), the compound shown in (16), the compound shown in (17), the compound shown in (18), the compound shown in (19), and the compound shown in (20) is included as a maleimide compound, from the viewpoint of obtaining better heat resistance and thermal stability, the total content of these maleimide compounds is preferably 10 to 90 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (C1) and these maleimide compounds, more preferably 20 to 70 parts by mass, further preferably 30 to 60 parts by mass, and even more preferably 35 to 55 parts by mass.

[0271] [Photocuring Initiator (D)]

[0272] The resin composition of this embodiment preferably further comprises a photocuring initiator (D) (also referred to as component (D) or initiator (D)). The photocuring initiator (D) is not particularly limited, and any substance commonly known in the field of photocurable resin compositions can be used. The photocuring initiator (D) is used to photocur the compound (A), compound (B), and, if necessary, maleimide compound (C) together using various active energy rays.

[0273] As photocuring initiators (D), examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl disperoxy phthalate; acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzoyl-diphenylphosphine oxide, and bisbenzoyl-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4] Acetophenones such as [-(methylthio)phenyl]-2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-pentylanthraquinone; thioxanones such as 2,4-diethylthioxanone, 2-isopropylthioxanone and 2-chlorothioxanone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal. Benzophenones, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-dimethylaminobenzophenone, etc.; oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime)] and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime), etc., are free radical photocuring initiators.

[0274] Diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate; sulfonium salts of Lewis acids such as triphenylsulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators; and other cationic photopolymerization initiators such as photoacid generators.

[0275] Photocuring initiators (D) can also be commercially available, such as: IGM Resins BV's Omnirad 369 (trade name), Omnirad 819 (trade name), Omnirad 819DW (trade name), Omnirad 907 (trade name), Omnirad TPO (trade name), Omnirad TPO-G (trade name), Omnirad 784 (trade name), and Irgacure OXE01 (trade name) from BASF JAPAN. Irgacure (registered trademark) OXE02 (trade name) manufactured by JAPAN, Irgacure (registered trademark) OXE03 (trade name) manufactured by BASF JAPAN, and Irgacure (registered trademark) OXE04 (trade name) manufactured by BASF JAPAN, etc.

[0276] These photocuring initiators (D) can be used alone or in appropriate combinations of two or more.

[0277] A chloroform solution containing 0.01% by mass of a photocurable initiator (D) was prepared. When the absorbance of the chloroform solution containing 0.01% by mass of the photocurable initiator (D) was measured using active energy rays containing a wavelength of 365 nm (i-rays), the absorbance was preferably 0.1 or higher, indicating that the photocurable initiator (D) exhibited very excellent absorbance. Furthermore, when the absorbance of the chloroform solution containing 0.01% by mass of the photocurable initiator (D) was measured using active energy rays containing a wavelength of 405 nm (h-rays), the absorbance was preferably 0.1 or higher, also exhibiting very excellent absorbance. When this photocurable initiator (D) is used, even when using active energy rays containing a wavelength of 405 nm (h-rays) to manufacture printed circuit boards with high-density and high-fine wiring formation (patterns), for example, direct-draw exposure methods, the photoradical reaction of maleimide occurs effectively. It should be noted that, from the perspective of obtaining a resin composition with superior photocurability, the absorbance at a wavelength of 365 nm (i-rays) is more preferably 0.15 or higher. From the perspective of obtaining a resin composition with superior photocurability, the absorbance at a wavelength of 405 nm (h-rays) is more preferably 0.15 or higher. It should be noted that the upper limits for the absorbance at wavelength 365 nm (i-rays) and the absorbance at wavelength 405 nm (h-rays) are, for example, 99.9 or lower.

[0278] From the viewpoint of having higher sensitivity relative to various active energy rays, oxime esters and acylphosphine oxides are preferred as photocuring initiators (D), with oxime esters being more preferred.

[0279] As an oxime ester, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyloxime) is preferred from the viewpoint that it has higher sensitivity and better solvent solubility compared to various active energy rays.

[0280] As an acylphosphine oxide, the compound shown in formula (28) is preferred from the perspective of having higher absorbance for various active energy rays, especially active energy rays containing i rays with a wavelength of 365 nm and active energy rays containing h rays with a wavelength of 405 nm.

[0281]

[0282] In equation (28), R 23 Each of the substituents or phenyl groups represented independently by formula (29) is represented by a substituent or phenyl group.

[0283]

[0284] In equation (29), R 24Each can independently represent a hydrogen atom or a methyl group. In formula (29), -* indicates a direct connection to R in formula (28). 23 The atomic bonds that connect the phosphorus atom (P).

[0285] Regarding the compound shown in formula (28), a chloroform solution containing 0.01% by mass of the compound was prepared. When the absorbance of the chloroform solution was measured using an active energy ray containing a wavelength of 365 nm (i-ray), the absorbance was 0.1 or higher, exhibiting very excellent absorbance for light with a wavelength of 365 nm (i-ray). Therefore, the compound suitably generates free radicals for light with a wavelength of 365 nm (i-ray). The absorbance is preferably 0.15 or higher. The upper limit is, for example, 10.0 or lower, but can be 5.0 or lower, or 2.0 or lower.

[0286] Regarding the compound shown in formula (28), when a chloroform solution containing 0.01% by mass of the compound was prepared, and the absorbance of the chloroform solution was measured using an active energy ray containing a wavelength of 405 nm (h-rays), the absorbance was 0.1 or higher, exhibiting very excellent absorbance for light with a wavelength of 405 nm (h-rays). Therefore, the compound suitably generates free radicals for light with a wavelength of 405 nm (h-rays). The absorbance is more preferably 0.15 or higher. The upper limit is, for example, 10.0 or lower, but can be 5.0 or lower, or 2.0 or lower.

[0287] In equation (28), R 23 Each of the substituents or phenyl groups represented independently by formula (29) is preferred. 23 One or more of them are substituents as shown in formula (29).

[0288] In equation (29), R 24 Each can independently represent a hydrogen atom or a methyl group. R is preferred. 24 One or more of them are methyl, more preferably all of them are methyl.

[0289] Examples of compounds represented by formula (28) include acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred from the viewpoint of having superior light transmittance. These compounds can be used alone or in appropriate combinations of two or more.

[0290] Acylphosphine oxides exhibit excellent light absorption for active energy rays containing a wavelength of 405 nm (h-rays). For example, maleimide compounds (C) can be suitably free-radicalized using wavelengths of 405 nm (h-rays). Therefore, according to this embodiment, it is possible to suitably manufacture resin compositions, resin sheets using the same, resin sheets, resin sheets, and semiconductor devices that exhibit excellent photocurability in the exposure process without hindering the photocuring reaction, particularly when used in multilayer printed circuit boards, and that impart excellent alkaline developability in the development process.

[0291] In the resin composition, from the viewpoint of enabling the resin composition to be photocured more fully without hindering the photocuring reaction, and to make the exposed portion more insoluble in terms of alkali developability, the content of photocuring initiator (D) is preferably 0.1 to 50 parts by mass of 100 parts by mass of resin solids in the resin composition, more preferably 0.2 to 30 parts by mass, even more preferably 0.3 to 10 parts by mass, and even more preferably 1.0 to 8.0 parts by mass.

[0292] Furthermore, when the resin composition contains both compound (A) and compound (B) and maleimide compound (C), from the viewpoint of enabling the resin composition to be photocured more fully without hindering the photocuring reaction and making the exposed portion more insoluble in terms of alkali developability, the content of photocuring initiator (D) is preferably 0.1 to 20 parts by mass relative to a total of 100 parts by mass of compound (A), compound (B), maleimide compound (C) and photocuring initiator (D), more preferably 0.2 to 15 parts by mass, even more preferably 0.3 to 10 parts by mass, and even more preferably 1.0 to 8.0 parts by mass.

[0293] [Filling material]

[0294] In the resin composition of this embodiment, a filler material can be used to further improve various properties such as film-forming properties and heat resistance. Preferably, the filler material is a material that has insulating properties and does not impede the transmission of various active energy rays used for photocuring.

[0295] Examples of filler materials include silica (such as natural silica, fused silica, amorphous silica, and hollow silica), aluminum compounds (such as boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride), boron compounds (such as boron nitride), magnesium compounds (such as magnesium oxide and magnesium hydroxide), calcium compounds (such as calcium carbonate), molybdenum compounds (such as molybdenum oxide and zinc molybdate), barium compounds (such as barium sulfate and barium silicate), talc (such as natural talc and calcined talc), mica, glass (such as short-fiber glass, spherical glass, micronized glass, E glass, T glass, and D glass), silicone powder, fluoropolymer fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber. These fillers can be used alone or in appropriate combinations of two or more.

[0296] Among these, preferably one or more are selected from the group consisting of silica, boehmite, barium sulfate, organosilicon powder, fluoropolymer filler, urethane resin filler, (meth)acrylic resin filler, polyethylene filler, styrene-butadiene rubber, and organosilicon rubber.

[0297] These filler materials can be surface-treated with silane coupling agents, etc., as described later.

[0298] From the viewpoint of further improving the heat resistance of the cured product and obtaining better coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include SFP-130MC (trade name) manufactured by Denka, SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by Admatechs.

[0299] The particle size of the filler material is not particularly limited, but from the viewpoint of further improving the ultraviolet light transmittance of the resin composition, it is generally 0.005 to 10 μm, preferably 0.01 to 1.0 μm.

[0300] In resin compositions, from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product, the content of filler material is generally preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less, relative to 100 parts by mass of the resin solids in the resin composition. It should be noted that, when filler material is included, from the viewpoint of obtaining effects that further improve coating properties, heat resistance, and other characteristics, the lower limit value is generally 1 part by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0301] [Silane coupling agents and wetting and dispersing agents]

[0302] In the resin composition of this embodiment, in order to further improve the dispersibility of the filler material and the adhesion strength between the polymer and / or the resin and the filler material, a combination of silane coupling agent and / or wetting and dispersing agent may be used.

[0303] As for these silane coupling agents, there are no particular limitations, mainly those commonly used in the surface treatment of inorganic materials. Examples include 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N [-dimethylamino)-propyl]trimethoxysilane and other aminosilane series; γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and [8-(glycidoxy)-n-octyl]trimethoxysilane and other epoxysilane series; vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane and trimethoxy... 4-Vinylphenyl)silanes and other vinylsilanes; 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyldiethoxymethylsilane and other methacryloylsilanes; 3-acryloyloxypropyltrimethoxysilane and 3-acryloyloxypropyltriethoxysilane and other acryloylsilanes; 3-isocyanopropyltrimethoxysilane and 3-isocyanopropyltriethoxysilane and other isocyanate silanes; tri-(trimethoxysilylpropyl)isocyanurate and other isocyanurate silanes; 3-mercaptopropyltrimethoxysilane The silane coupling agents include mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane; ureosilanes such as 3-ureopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl-γ-aminopropyltrimethoxysilane hydrochloride); acid anhydride systems such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; and arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in appropriate combinations of two or more.

[0304] In resin compositions, the content of silane coupling agent is typically 0.1 to 10 parts by weight relative to 100 parts by weight of the solid resin component in the resin composition.

[0305] As a wetting and dispersing agent, there are no particular limitations as long as it is a dispersing stabilizer used in coating applications. Specific examples include BYK Japan's DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, and W903 (trade names). These wetting and dispersing agents can be used alone or in appropriate combinations of two or more.

[0306] In resin compositions, the content of wetting and dispersing agents is typically 0.1 to 10 parts by weight relative to 100 parts by weight of the resin solids in the resin composition.

[0307] [Cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds]

[0308] In this embodiment, as long as the effects of the present invention are achieved, various compounds and resins, excluding compounds (A), (B), maleimide compounds (C), and photocuring initiators (D), such as cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds, can be used based on the flame retardancy, heat resistance, and thermal expansion characteristics of the cured product. Furthermore, regarding these compounds and resins, it is preferable that the resin composition undergoes photocuring upon exposure to various active energy rays, particularly active energy rays containing a wavelength of 365 nm (i-rays) and active energy rays containing a wavelength of 405 nm (h-rays).

[0309] These compounds and resins can be used alone or in appropriate combinations of two or more.

[0310] <Cyanate compounds>

[0311] As a cyanate compound, there are no particular limitations as long as it is a resin having an aromatic moiety that is substituted with at least one cyanooxy group (cyanate group) in the molecule.

[0312] Examples of compounds can be listed, such as those shown in formula (30).

[0313]

[0314] In formula (30), Ar1 represents a benzene ring, a naphthalene ring, or a group consisting of two benzene rings bonded by a single bond. Multiple Ar1 groups may be identical or different. Ra independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an aryl group with 6 to 12 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a group consisting of an alkyl group with 1 to 6 carbon atoms bonded to an aryl group with 6 to 12 carbon atoms. The aromatic ring in Ra may optionally have substituents, and the substituents in Ar1 and Ra may be in any position. p represents the number of cyanoxy groups bonded to Ar1, each being an integer from 1 to 3. q represents the number of Ra groups bonded to Ar1, which is 4-p when Ar1 is a benzene ring, 6-p when Ar1 is a naphthalene ring, and 8-p when Ar1 is a group consisting of two benzene rings bonded by a single bond. t represents the average number of repetitions, an integer from 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t values. In the presence of multiple X's, each X independently represents a single bond, a divalent organic group with 1 to 50 carbon atoms (with hydrogen atoms optionally replaced by heteroatoms), a divalent organic group with 1 to 10 nitrogen atoms (e.g., -NRN-, where R represents an organic group), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyl dioxy group (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom, or a divalent oxygen atom.

[0315] The alkyl group in Ra of formula (30) can have either a straight or branched chain structure, or a cyclic structure (such as cycloalkyl).

[0316] In addition, the hydrogen atoms in the alkyl group and the aryl group in formula (30) may be optionally replaced by halogen atoms such as fluorine and chlorine atoms, alkoxy groups such as methoxy and phenoxy groups, or cyano groups.

[0317] Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl.

[0318] Specific examples of alkenyl groups include vinyl, (methyl)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl, 2-pentenyl, and 2-hexenyl.

[0319] Specific examples of aryl groups include phenyl, xylyl, mesitylene, naphthyl, phenoxyphenyl, ethylphenyl, o-fluorophenyl, m-fluorophenyl or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl and o-tolyl, m-tolyl or p-tolyl, etc.

[0320] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy.

[0321] Specific examples of divalent organic groups with 1 to 50 carbon atoms in X of formula (30) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenyl-dimethylmethylene, fluorenediyl, and phthalidediyl. The hydrogen atoms in the divalent organic group may be optionally replaced by halogen atoms such as fluorine and chlorine atoms, alkoxy groups such as methoxy and phenoxy groups, and cyano groups.

[0322] Examples of divalent organic groups with nitrogen number 1 to 10 in X of formula (30) include imino and polyimide groups.

[0323] In addition, as an organic group of X in formula (30), examples include groups having the structure shown in formula (31) or groups having the structure shown in formula (32).

[0324]

[0325] In formula (31), Ar2 represents phenyldiyl, naphthyl, or biphenyldiyl, and they may be the same or different from each other when u is an integer of 2 or more. Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxyl group. Rd and Re each independently select from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer from 0 to 5.

[0326]

[0327] In formula (32), Ar3 represents phenyldiyl, naphthyl, or biphenyldiyl, which may be the same or different from each other when v is an integer of 2 or more. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least one cyanoxy group. v represents an integer of 0 to 5, or may be a mixture of compounds with different v.

[0328] Furthermore, as X in formula (30), divalent groups can be listed as shown in the following formula.

[0329]

[0330] Here, z represents an integer from 4 to 7. Rk independently represents either a hydrogen atom or an alkyl group with 1 to 6 carbon atoms.

[0331] As specific examples of Ar2 in formula (31) and Ar3 in formula (32), examples include phenyldiyl groups with two carbon atoms as shown in formula (31) or two oxygen atoms as shown in formula (32) bonded to the 1,4 or 1,3 positions; biphenyldiyl groups with two carbon atoms or two oxygen atoms bonded to the 4,4', 2,4', 2,2', 2,3', 3,3' or 3,4' positions; and naphthyl groups with two carbon atoms or two oxygen atoms bonded to the 2,6, 1,5, 1,6, 1,8, 1,3, 1,4 or 2,7 positions.

[0332] The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg in formula (31) and Ri and Rj in formula (32) have the same meaning as in formula (30).

[0333] Specific examples of cyanoxy-substituted aromatic compounds represented by formula (30) include cyanoxybenzene, 1-cyanoxy-2-methylbenzene, 1-cyanoxy-3-methylbenzene or 1-cyanoxy-4-methylbenzene, 1-cyanoxy-2-methoxybenzene, 1-cyanoxy-3-methoxybenzene or 1-cyanoxy-4-methoxybenzene, 1-cyanoxy-2,3-dimethylbenzene, 1-cyanoxy-2,4-dimethylbenzene, 1-cyanoxy-2,5-dimethylbenzene, 1-cyanoxy-2,6-dimethylbenzene, 1-cyanoxy-3,4-dimethylbenzene or 1-cyanoxy-3,5-dimethylbenzene, cyanoxy-ethylbenzene, cyanoxy-butylbenzene, cyanoxy-octylbenzene, cyanoxy-nonylbenzene, 2-(4-cyanoxyphenyl)-2-phenylpropane (4- α-Cyanocyanate of cumylphenol), 1-cyanooxy-4-cyclohexylbenzene, 1-cyanooxy-4-vinylbenzene, 1-cyanooxy-2-chlorobenzene or 1-cyanooxy-3-chlorobenzene, 1-cyanooxy-2,6-dichlorobenzene, 1-cyanooxy-2-methyl-3-chlorobenzene, cyanooxynitrobenzene, 1-cyanooxy-4-nitro-2-ethylbenzene, 1-cyanooxy-2-methoxy-4-allylbenzene (cyanocyanate of eugenol), methyl (4-cyanooxyphenyl) sulfide, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2- or 1-cyanooxy-4-acetylbenzene, 4-cyanooxybenzaldehyde, methyl 4-cyanooxybenzoate, phenyl 4-cyanooxybenzoate, 1-cyanooxy-4-acetaminophen, 4 1-Cyanoxybenzophenone, 1-Cyanoxy-2,6-di-tert-butylbenzene, 1,2-Dicyanoxybenzene, 1,3-Dicyanoxybenzene, 1,4-Dicyanoxybenzene, 1,4-Dicyanoxy-2-tert-butylbenzene, 1,4-Dicyanoxy-2,4-dimethylbenzene, 1,4-Dicyanoxy-2,3,4-dimethylbenzene, 1,3-Dicyanoxy-2,4,6-trimethylbenzene, 1,3-Dicyanoxy-5-methylbenzene, 1-Cyanoxy or 2-Cyanoxynaphthalene, 1-Cyanoxy-4-methoxynaphthalene, 2-Cyanoxy-6-methoxynaphthalene, 2-Cyanoxy-7-methoxynaphthalene, 2,2'-Dicyanoxy-1,1'-Binaphthalene, 1,3-Dicyanoxynaphthalene, 1,4-Dicyanoxynaphthalene, 1,5-Dicyanoxynaphthalene, 1,6- Dicyanooxynaphthalene, 1,7-dicyanooxynaphthalene, 2,3-dicyanooxynaphthalene, 2,6-dicyanooxynaphthalene or 2,7-dicyanooxynaphthalene, 2,2'-dicyanooxybiphenyl or 4,4'-dicyanooxybiphenyl, 4,4'-dicyanooxyoctafluorobiphenyl, 2,4'-dicyanooxydiphenylmethane or 4,4'-dicyanooxydiphenylmethane, bis(4-cyanooxy-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanooxyphenyl)ethane, 1,1-bis(4-cyanooxyphenyl)propane, 2,2-bis(4-cyanooxyphenyl)propane, 2,2-bis(4-cyanooxy-3-methylphenyl)propane, 2,2-bis(2-cyanooxy-5-biphenyl)propane, 2,2-bis(4-cyanooxyphenyl)hexafluoropropane, 2,2-bis(4-cyanoxy-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanoxyphenyl)butane, 1,1-bis(4-cyanoxyphenyl)isobutane, 1,1-bis(4-cyanoxyphenyl)pentane, 1,1-bis(4-cyanoxyphenyl)-3-methylbutane, 1,1-bis(4-cyanoxyphenyl)-2-methylbutane, 1,1-bis(4-cyanoxyphenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanoxyphenyl)butane, 2,2-bis(4-cyanoxyphenyl)pentane, 2,2-bis(4-cyanoxyphenyl)hexane, 2,2-bis(4-cyanoxyphenyl)-3-methylbutane, 2,2-bis(4-cyanoxyphenyl)-4-methylpentane, 2,2-bis... (4-Cyanoxyphenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanoxyphenyl)hexane, 3,3-bis(4-cyanoxyphenyl)heptane, 3,3-bis(4-cyanoxyphenyl)octane, 3,3-bis(4-cyanoxyphenyl)-2-methylpentane, 3,3-bis(4-cyanoxyphenyl)-2-methylhexane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanoxyphenyl)-3-methylheptane, 3,3-bis(4-cyanoxyphenyl)-2-methylheptane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylhexane, 2,2,4-Trimethylpentane, 2,2-bis(4-cyanoxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanoxyphenyl)phenylmethane, 1,1-bis(4-cyanoxyphenyl)-1-phenylethane, bis(4-cyanoxyphenyl)biphenylmethane, 1,1-bis(4-cyanoxyphenyl)cyclopentane, 1,1-bis(4-cyanoxyphenyl)cyclohexane, 2,2-bis(4-cyanoxy-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanoxyphenyl)cyclohexane, bis(4-cyanoxyphenyl)diphenylmethane, bis(4-cyanoxyphenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanoxyphenyl)-2-propyl]benzene 1,4-bis[2-(4-cyanoxyphenyl)-2-propyl]benzene, 1,1-bis(4-cyanoxyphenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanoxyphenyl)methyl]biphenyl, 4,4-dicyanoxybenzophenone, 1,3-bis(4-cyanoxyphenyl)-2-propen-1-one, bis(4-cyanoxyphenyl) ether, bis(4-cyanoxyphenyl) sulfide, bis(4-cyanoxyphenyl) sulfone, 4-cyanoxybenzoic acid-4-cyanoxyphenyl ester (4-cyanoxyphenyl-4-cyanoxybenzoate), bis-(4-cyanoxyphenyl) carbonate, 1,3-bis(4-cyanoxyphenyl)adamantane, 1,3-bis(4-cyanoxyphenyl)-5,7-dimethyladamantane, 3,3-Bis(4-cyanoxyphenyl)isobenzofuran-1(3H)-one (cyanate ester of phenolphthalein), 3,3-bis(4-cyanoxy-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate ester of o-cresolphthalein), 9,9'-bis(4-cyanoxyphenyl)fluorene, 9,9-bis(4-cyanoxy-3-methylphenyl)fluorene, 9,9-bis(2-cyanoxy-5-biphenyl)fluorene, tris(4-cyanoxyphenyl)methane, 1,1,1-tris(4-cyanoxyphenyl)methane α,α,α'-tris(4-cyanooxyphenyl)ethane, 1,1,3-tris(4-cyanooxyphenyl)propane, α,α,α'-tris(4-cyanooxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetra(4-cyanooxyphenyl)ethane, tetra(4-cyanooxyphenyl)methane, 2,4,6-tris(N-methyl-4-cyanooxyaniline)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanooxyaniline)-6-(N-methylaniline)- 1,3,5-Triazine, bis(N-4-cyanoxy-2-methylphenyl)-4,4'-oxophthalimide, bis(N-3-cyanoxy-4-methylphenyl)-4,4'-oxophthalimide, bis(N-4-cyanoxyphenyl)-4,4'-oxophthalimide, bis(N-4-cyanoxy-2-methylphenyl)-4,4'-(hexafluoroisopropyl)diphthalimide, tris(3,5-dimethyl-4-cyanoxy) Benzyl isocyanurate, 2-phenyl-3,3-bis(4-cyanoxyphenyl)benzo[C]pyrrolidone, 2-(4-methylphenyl)-3,3-bis(4-cyanoxyphenyl)benzo[C]pyrrolidone, 2-phenyl-3,3-bis(4-cyanoxyphenyl)benzo[C]pyrrolidone, 1-methyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one and 2-phenyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one.

[0334] These cyanate compounds can be used alone or in appropriate combinations of two or more.

[0335] Other specific examples of the cyanate ester compounds shown in formula (30) include: phenol-formaldehyde varnish resins and cresol-formaldehyde varnish resins (substances obtained by reacting phenol, alkyl-substituted phenol, or halogen-substituted phenol with formaldehyde compounds such as formaldehyde or paraformaldehyde in an acidic solution using known methods), triphenol-formaldehyde varnish resins (substances obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), and fluorene-formaldehyde varnish resins (substances obtained by reacting fluorene ketone compounds with 9,9-bis(hydroxyaryl)fluorenes in an acidic solution). Substances obtained by reacting in the presence of an acidic catalyst), phenolic aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, and biphenyl aralkyl resins (substances obtained by reacting a dihalomethyl compound as shown in Ar4-(CH2Y)2 (Ar4 represents phenyl, Y represents a halogen atom. The same applies hereinafter in this paragraph) with a phenolic compound using a known method, either in the presence or without a catalyst; bis(alkoxymethyl) compounds as shown in Ar4-(CH2OR)2 (R represents alkyl). Substances obtained by reacting a bis(hydroxymethyl) compound with a phenolic compound in the presence of an acidic catalyst; or substances obtained by reacting a bis(hydroxymethyl) compound, such as Ar4-(CH2OH)2, with a phenolic compound in the presence of an acidic catalyst; or substances obtained by condensing an aromatic aldehyde compound with an aralkyl compound and a phenolic compound; phenol-modified xyleneformaldehyde resin (substance obtained by reacting xyleneformaldehyde resin with a phenolic compound in the presence of an acidic catalyst using a known method); modified naphthaldehyde resin (substance obtained by reacting naphthaldehyde resin with a hydroxyl-substituted aromatic compound in the presence of an acidic catalyst using a known method); phenol-modified dicyclopentadiene resin or phenolic resin having a polynaphthalene ether structure (substance obtained by dehydrating and condensing a polyhydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of an alkaline catalyst using a known method); and other phenolic resins obtained by cyanate esterification using the same methods as described above, as well as their prepolymers. These cyanate ester compounds can be used alone or in appropriate combinations of two or more.

[0336] There are no particular limitations on the method for producing these cyanate ester compounds, and known methods can be used. Specific examples include purchasing or synthesizing hydroxyl-containing compounds with a desired skeleton and modifying the hydroxyl groups using known methods to induce cyanate esterification. Methods for inducing cyanate esterification of hydroxyl groups include, for example, those described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

[0337] Cured products using these cyanate compounds exhibit superior properties such as glass transition temperature, low thermal expansion, and coating adhesion.

[0338] When the resin composition contains maleimide compound (C), the content of cyanate compound is 0.01 to 40 parts by mass relative to the total of 100 parts by mass of maleimide compound (C) and cyanate compound.

[0339] Phenolic resin

[0340] As for phenolic resins, any phenolic resin having two or more hydroxyl groups in one molecule can use commonly known substances. Examples of phenolic resins include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenolic varnish resin, bisphenol A phenolic varnish type phenolic resin, glycidyl ester type phenolic resin, aralkyl phenolic varnish type phenolic resin, biphenyl aralkyl type phenolic resin, cresol phenolic varnish type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol phenolic varnish resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic varnish type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, phenolic resin containing polymerizable unsaturated hydrocarbon groups, and hydroxyl-containing organosilicon resins. These phenolic resins can be used alone or in appropriate mixtures of two or more.

[0341] When the resin composition contains maleimide compound (C), the content of phenolic resin is 0.01 to 40 parts by mass relative to the total 100 parts by mass of maleimide compound (C) and phenolic resin.

[0342] <Oxycyclobutane resin>

[0343] As oxetane resins, commonly known substances can be used. Examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toa Synthetic Co., Ltd., trade name), OXT-121 (manufactured by Toa Synthetic Co., Ltd., trade name), and OXT-221 (manufactured by Toa Synthetic Co., Ltd., trade name), etc. These oxetane resins can be used alone or in appropriate mixtures of two or more.

[0344] When the resin composition contains maleimide compound (C), the content of oxetane resin is 0.01 to 40 parts by mass relative to the total 100 parts by mass of maleimide compound (C) and phenolic resin.

[0345] <Benzoxazine compounds>

[0346] As benzoxazine compounds, any compound having two or more dihydrobenzoxazine rings in one molecule can use commonly known substances. Examples include bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), Pd type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), Fa type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), and phenolphthalein type benzoxazine, etc. These benzoxazine compounds can be used alone or in appropriate combinations of two or more.

[0347] When the resin composition contains maleimide compound (C), the content of benzoxazine compound is 0.01 to 40 parts by mass relative to the total 100 parts by mass of maleimide compound (C) and benzoxazine compound.

[0348] <Epoxy Resin>

[0349] There are no particular limitations on epoxy resins; commonly known substances can be used. Examples include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A phenolic varnish epoxy resin, biphenyl type epoxy resin, phenolic varnish epoxy resin, cresol phenolic varnish epoxy resin, xylene phenolic varnish epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic varnish epoxy resin, naphthalene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, and so on. Hydroglyceride-type epoxy resins, alicyclic epoxy resins, dicyclopentadiene phenolic varnish-type epoxy resins, biphenyl phenolic varnish-type epoxy resins, phenol aralkyl phenolic varnish-type epoxy resins, naphthol aralkyl phenolic varnish-type epoxy resins, aralkyl phenolic varnish-type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds obtained by epoxidation of the double bonds of butadiene, etc., compounds obtained by the reaction of hydroxyl-containing organosilicon resins with epichlorohydrin, and their halides. These epoxy resins can be used alone or in appropriate mixtures of two or more.

[0350] As epoxy resin, commercially available products can be used, such as epoxy resin shown in formula (33) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., n5 is about 4 in formula (33)) and naphthalene-type epoxy resin shown in formula (34) (HP-4710 (trade name) manufactured by DIC Co., Ltd.).

[0351]

[0352] These epoxy resins can be used alone or in appropriate combinations of two or more.

[0353] When the resin composition contains maleimide compound (C), the content of epoxy resin is 0.01 to 40 parts by mass relative to 100 parts by mass of the total of maleimide compound (C) and epoxy resin.

[0354] <Other Compounds>

[0355] Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrene compounds such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; and triallyl isocyanurate, trimethylallyl isocyanurate, and diallyl nadicimide. These compounds can be used alone or in appropriate combinations of two or more.

[0356] When the resin composition contains maleimide compound (C), the content of other compounds is 0.01 to 40 parts by mass relative to the total of 100 parts by mass of maleimide compound (C) and other compounds.

[0357] [Organic solvents]

[0358] The resin composition of this embodiment may contain an organic solvent as needed. Using an organic solvent allows for adjustment of the viscosity during the preparation of the resin composition. There are no particular limitations on the type of organic solvent, as long as it can dissolve some or all of the resin in the resin composition. Examples of organic solvents include halogenated solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosol solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; and aromatic hydrocarbon solvents such as toluene and xylene.

[0359] From the viewpoint that they also exhibit superior solubility for compounds (A) and (B), compounds (C) mixed as needed, photocuring initiator (D), and other resins and compounds, aprotic polar solvents, ketone solvents, cellosol solvents, and ester solvents are preferred, and from the viewpoint that they exhibit superior solubility, aprotic polar solvents, ketone solvents, and ester solvents are more preferred.

[0360] Dimethylacetamide is preferred as an aprotic polar solvent. Methyl ethyl ketone is preferred as a ketone solvent. Propylene glycol monomethyl ether is preferred as a cellosol solvent. Butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred as ester solvents.

[0361] These organic solvents can be used alone or in appropriate combinations of two or more.

[0362] [Other ingredients]

[0363] In the resin composition of this embodiment, various polymeric compounds such as thermosetting resins, thermoplastic resins and their oligomers, and elastomers not mentioned above may be used in combination without impairing the characteristics of this embodiment; flame-retardant compounds not mentioned above; additives, etc. These are not particularly limited as long as they are commonly used substances. For example, flame-retardant compounds may include nitrogen-containing compounds such as melamine and benzoguanamine; compounds containing oxazine rings; phosphorus-based compounds such as phosphate esters, aromatic condensed phosphate esters, and halogenated condensed phosphate esters. Additives may include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, and thermosetting accelerators. These components may be used individually or in appropriate combinations of two or more.

[0364] In a resin composition, the content of other components is typically 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0365] [Method for manufacturing resin composition and varnish]

[0366] The resin composition of this embodiment can be prepared by appropriately mixing compounds (A) and (B), a maleimide compound (C) as needed, a photocuring initiator (D), fillers, and other resins, other compounds, and additives. Regarding the method of manufacturing the resin composition, for example, a method in which the aforementioned components are sequentially mixed in a solvent and thoroughly stirred.

[0367] When manufacturing a resin composition, known treatments (stirring, mixing, and kneading, etc.) for uniformly dissolving or dispersing the components can be performed as needed. Specifically, by using a stirring tank equipped with a stirrer having appropriate stirring capacity, the dispersibility of components such as compound (A) and compound (B) in the resin composition can be improved. Stirring, mixing, and kneading can be performed appropriately using known devices such as stirring apparatus for dispersion (e.g., ultrasonic homogenizer), mixing apparatus for mixing (e.g., three-roll mill, ball mill, bead mill, and sand mill), or rotary or self-rotating mixing apparatus. Furthermore, organic solvents can be used as needed when preparing the resin composition. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition; specific examples are as described above.

[0368] The resin composition can be suitably used in the form of a varnish for making the resin sheet described in this embodiment later. The varnish can be obtained by known methods. For example, the varnish can be obtained by adding 10 to 900 parts by weight, preferably 30 to 500 parts by weight, of an organic solvent relative to 100 parts by weight of the components other than the organic solvent in the resin composition, and performing the aforementioned known treatment (stirring, mixing, and kneading, etc.). It should be noted that the organic solvent used to prepare the varnish is not particularly limited, and specific examples are as described above.

[0369] [use]

[0370] The resin composition of this embodiment can be suitably used to manufacture multilayer printed circuit boards, and is preferably used for applications requiring an insulating resin composition. It can be used, for example, in photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminate applications, multilayer printed circuit board applications, etc.), solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, via-filling resins, and component-filling resins. Among these, the resin composition exhibits excellent photocurability and alkaline developability, therefore, it can be suitably used for insulating layers or solder resist applications in multilayer printed circuit boards.

[0371] [cured material]

[0372] A cured product is obtained by curing a resin composition. For example, a cured product can be obtained by melting or dissolving the resin composition in a solvent, pouring it into a mold, and then curing it under normal conditions using light. Regarding the wavelength range of the light, curing is preferably carried out in the range of 100–500 nm, where curing is highly efficient using photopolymerization initiators or the like.

[0373] [Resin Sheet]

[0374] The resin sheet of this embodiment is a resin sheet with a support, having a support and a resin layer disposed on one or both sides of the support, the resin layer containing the resin composition of this embodiment. The resin sheet can be manufactured by coating the resin composition onto the support and drying it. The resin layer in the resin sheet has excellent photocurability and alkali developability.

[0375] The support can be any known support, without particular limitation, but a resin film is preferred. Examples of resin films include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, polyethylene naphthalate films, polyvinyl alcohol films, and triacetyl acetate films. Among these, PET films are preferred.

[0376] To facilitate peeling from the resin layer, the resin film is preferably coated with a release agent on its surface. The thickness of the resin film is preferably in the range of 5 to 100 μm, more preferably in the range of 10 to 50 μm. When the thickness is less than 5 μm, the support tends to break easily during support peeling before alkaline development; when the thickness exceeds 100 μm, there is a tendency for reduced resolution during exposure from the support. In this specification, the thickness can be measured using, for example, a micrometer.

[0377] In addition, to reduce light scattering during exposure, the resin film is preferably highly transparent.

[0378] Furthermore, in the resin sheet, the resin layer can be protected with a protective film.

[0379] By protecting the resin layer with a protective film, it is possible to prevent the adhesion and / or scratching of dust and other contaminants to the surface of the resin layer. The protective film can be made of the same material as the resin film. The thickness of the protective film is preferably in the range of 1 to 50 μm, more preferably in the range of 5 to 40 μm. When the thickness is less than 1 μm, the processability of the protective film tends to decrease; when it exceeds 50 μm, its cost-effectiveness tends to deteriorate. It should be noted that, regarding the protective film, it is preferable that the adhesion strength between the resin layer and the protective film is less than the adhesion strength between the resin layer and the support.

[0380] Methods for manufacturing resin sheets include, for example, coating a resin composition onto a support such as a PET film, drying it to remove organic solvents, and thus manufacturing a resin sheet.

[0381] Regarding the coating method, it can be carried out using known methods such as roller coaters, comma coaters, gravure coaters, die coaters, bar coaters, lip coaters, doctor blade coaters, and extrusion coaters. Drying can be carried out, for example, by heating in a dryer at 60–200°C for 1–60 minutes.

[0382] From the viewpoint of further preventing the diffusion of organic solvents in subsequent processes, the amount of organic solvent remaining in the resin layer is preferably set to 5% by mass or less relative to the total mass of the resin layer. From the viewpoint of improving processability, the thickness of the resin layer is preferably set to 1 to 50 μm.

[0383] Resin sheets are preferably used in the manufacture of insulating layers for multilayer printed circuit boards.

[0384] Multilayer printed circuit boards

[0385] The multilayer printed circuit board of this embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer. The insulating layer contains the resin composition of this embodiment. The insulating layer can also be obtained, for example, by overlapping one or more resin sheets and curing them. The number of layers for the insulating layer and the conductor layer can be appropriately set according to the intended use. Furthermore, the order of the insulating layer and the conductor layer is not particularly limited. The conductor layer can be a metal foil used in various printed circuit board materials, such as copper and aluminum foil. Examples of copper foils include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is typically 1 to 100 μm. Specifically, it can be manufactured by the following method.

[0386] (Lamination process)

[0387] In the lamination process, a vacuum laminator is used to laminate the resin layer side of the resin sheet onto one or both sides of the circuit board. Examples of circuit boards include glass epoxy boards, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. It should be noted that a circuit board refers to a substrate on one or both sides of the substrate described above where a patterned conductor layer (circuit) is formed. Furthermore, in multilayer printed circuit boards (PCBs) formed by alternating layers of conductor and insulating layers, the outermost layer of the PCB with one or both sides having a patterned conductor layer (circuit) is also included within the category of circuit boards. It should be noted that the insulating layer laminated in a multilayer PCB can be an insulating layer obtained by overlapping and curing one or more resin sheets of this embodiment, or an insulating layer obtained by overlapping one or more resin sheets of this embodiment and a known resin sheet different from the resin sheet of this embodiment. It should be noted that the overlapping method of the resin sheet in this embodiment and a known resin sheet different from that in this embodiment is not particularly limited. Roughening treatment can be performed beforehand by pre-performing a blackening treatment and / or copper etching on the surface of the conductor layer. In the lamination process, if the resin sheet has a protective film, after the protective film is peeled off, the resin sheet and the circuit board are preheated as needed, and the resin layer of the resin sheet is pressed onto the circuit board while under pressure and heat. In this embodiment, a method of laminating the resin layer of the resin sheet onto the circuit board under reduced pressure using a vacuum lamination method is suitable.

[0388] Regarding the conditions for the lamination process, the preferred options are, for example, setting the pressing temperature (lamination temperature) to 50–140℃ and the pressing pressure to 1–15 kgf / cm². 2 The lamination time is set to 5–300 seconds, and lamination is performed under reduced air pressure of 20 mmHg or less. Furthermore, the lamination process can be intermittent or continuous using rollers. Vacuum lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include, for instance, the two-stage lamination laminator manufactured by NIKKO MATERIALS.

[0389] (Exposure process)

[0390] In the exposure process, after a resin layer is deposited on the circuit board through a lamination process, a designated portion of the resin layer is irradiated with various active energy rays, which serve as a light source, causing the resin layer in the irradiated portion to cure. Compound (A) does not interfere with the photocuring reaction during the exposure process.

[0391] Irradiation can be achieved through mask patterns or by direct irradiation. Examples of active energy rays include ultraviolet light, visible light, electron beams, and X-rays. The wavelengths of active energy rays are, for example, in the range of 200–600 nm. When using ultraviolet light, the irradiation dose is approximately 5–1000 mJ / cm². 2 Furthermore, when manufacturing printed circuit boards with high-density and high-precision wiring formation (patterning) using a step-projection lithography machine that performs projection exposure in a step-by-step repeating manner, it is preferable to use, for example, an active energy beam containing a wavelength of 365 nm (i-ray) as the active energy beam. When using an active energy beam containing a wavelength of 365 nm (i-ray), the irradiation dose is approximately 5 to 10,000 mJ / cm². 2 When using direct-draw exposure to manufacture printed circuit boards with high-density and high-fineness wiring formation (patterning), active energy rays containing, for example, a wavelength of 405 nm (h-rays) are preferably used as the active energy rays. When using active energy rays containing a wavelength of 405 nm (h-rays), the irradiation dose is approximately 5 to 10,000 mJ / cm². 2 .

[0392] Among the exposure methods using mask patterns, there are contact exposure methods where the mask pattern is tightly adhered to a multilayer printed circuit board; and non-contact exposure methods where the mask pattern is not tightly adhered but projected using lenses or mirrors. Either method can be used. Furthermore, if a support is present on the resin layer, exposure can be performed from the support or after the support has been peeled off.

[0393] (Alkali development process)

[0394] In the absence of a support on the resin layer, after the exposure process, the uncured portion (unexposed portion) can be removed directly by alkaline development, and then development can be performed to form the pattern of the insulating layer.

[0395] In addition, when a support is present on the resin layer, after the exposure process, the uncured portion (unexposed portion) can be removed by alkaline development after the support is removed, and then development can be performed to form a pattern of the insulating layer.

[0396] The unexposed resin layer containing the resin composition of this embodiment contains compounds (A) and (B), and therefore exhibits excellent alkaline developability, enabling rapid removal of the unexposed resin composition. Consequently, printed circuit boards with highly detailed patterns can be obtained.

[0397] In the case of alkaline development, there are no particular limitations on the developer as long as it selectively washes away the unexposed portions; alkaline developers such as tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution can be used. In this embodiment, tetramethylammonium hydroxide aqueous solution is more preferred. These alkaline developers can be used alone or in appropriate combinations of two or more.

[0398] In addition, as an alkaline development method, known methods such as immersion, agitation, spraying, shaking immersion, brushing, and scraping can be used. These development methods can also be combined as needed during pattern formation. Furthermore, as a development method, high-pressure spraying is suitable for further improving resolution. The spray pressure when using a spraying method is preferably 0.02 to 0.5 MPa.

[0399] (Post-baking process)

[0400] In this embodiment, a post-baking process is performed after the alkaline development step to form an insulating layer (cured material). Examples of post-baking processes include ultraviolet irradiation using a high-pressure mercury lamp and heating using a cleanroom oven; combinations of these methods are also possible. When irradiating with ultraviolet light, the irradiation dose can be adjusted as needed, for example, from 0.05 to 10 J / cm². 2 Irradiation is performed at approximately the same level. Furthermore, heating conditions can be appropriately selected as needed, preferably within the range of 150–220°C for 20–180 minutes, and more preferably within the range of 160–200°C for 30–150 minutes.

[0401] (Conductor layer formation process)

[0402] After the insulating layer (cured material) is formed, a conductor layer is formed on the surface of the insulating layer by dry plating.

[0403] It should be noted that, when forming the conductor layer, the surface of the insulating layer can be modified before dry plating. Known methods such as plasma etching, reverse sputtering, and corona treatment can be used for surface modification.

[0404] As a dry plating process, known methods such as vapor deposition, sputtering, and ion plating can be used. Regarding vapor deposition (vacuum vapor deposition), a metal film can be formed on an insulating layer by, for example, placing a multilayer printed circuit board in a vacuum container and heating and evaporating the metal. Regarding sputtering, a metal film can also be formed on an insulating layer by, for example, placing a multilayer printed circuit board in a vacuum container, introducing an inert gas such as argon, and applying a DC voltage, causing the ionized inert gas to bombard a target metal, and using the ejected metal to form a metal film on the insulating layer.

[0405] Next, a conductor layer is formed by chemical plating, electroplating, or other methods. Subsequent patterning methods can include subtractive or semi-additive processes.

[0406] [Semiconductor Devices]

[0407] The semiconductor device of this embodiment comprises the resin composition of this embodiment. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed circuit board. Here, a conductive portion refers to a portion of the multilayer printed circuit board that transmits electrical signals; its location can be on the surface or in a filled portion. Furthermore, the semiconductor chip is not particularly limited as long as it is a circuit element made of semiconductor material.

[0408] There are no particular limitations on the mounting methods for semiconductor chips during the manufacture of semiconductor devices, as long as the semiconductor chip functions effectively. Specifically, examples include wire bonding mounting methods, flip chip mounting methods, bump-free uplift (BBUL) mounting methods, anisotropic conductive film (ACF) mounting methods, and non-conductive film (NCF) mounting methods.

[0409] Alternatively, semiconductor devices can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or on a substrate on which the semiconductor chip is mounted. The substrate on which the semiconductor chip is mounted can be in the shape of a wafer or a panel. It can be manufactured using the same method as the aforementioned multilayer printed circuit board after its formation.

[0410] Example

[0411] The present embodiment will now be described in more detail using examples and comparative examples. This embodiment is not limited in any way by the examples described below.

[0412] Synthesis of maleimide compound (TMDM)

[0413] [Synthesis example 1]

[0414] The compound (TMDM) shown in formula (21) is synthesized as follows.

[0415] Synthesis of Amide Acid Compounds (hereinafter referred to as MA-TMDA)

[0416] First, the MA-TMDA shown in formula (35) is synthesized using the following method.

[0417]

[0418] Add 5.2 g (53 mmol) of maleic anhydride, 20 mL of N-methylpyrrolidone (NMP), and 20 mL of toluene to a 100 mL four-necked flask equipped with an argon inlet, a Dean-Stark apparatus, a serpentine condenser, and a thermometer. Stir at room temperature (25 °C) under an argon gas flow until the maleic anhydride is completely dissolved. Add 5.0 g (19 mmol) of TMDA (a mixture of 5-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indane and 6-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indane, manufactured by Junra Pharmaceutical Co., Ltd. of Japan) and 10 mL of NMP to the solution. Stir at room temperature (25 °C) for 17 hours.

[0419] A portion of the reaction solution was removed, and water and ethyl acetate were added, followed by shaking. The organic layer was then removed and dried over magnesium sulfate. The supernatant was distilled off at 40°C to obtain a yellow oil. 1 H-NMR measurements confirmed that it was MA-TMDA as shown in formula (35).

[0420] The following shows the MA-TMDA represented by equation (35). 1 The assignment of H-NMR. Additionally, 1 The H-NMR spectrum is shown in Figure 1 .

[0421] 1 H-NMR (300MHz, DMSO-d6) δ (ppm): 10.40 (m, 2H, -COOH), 7.30 (m, 7H, ArH), 6.33 (m, 4H ,=CH-), 2.11(m, 2H, -CH2-), 1.48(d, 3H, -CH3), 1.21(d, 3H, -CH3), 0.92(d, 3H, -CH3)

[0422] [Synthesis of TMDM]

[0423] 0.67 g (3.5 mmol) of p-toluenesulfonic acid monohydrate was added to the aforementioned reaction solution, and the mixture was heated under reflux at 127 °C for 2.5 hours. After cooling to room temperature (25 °C), the cooled reaction solution was added, while stirring, to a mixture of 50 mL of saturated sodium bicarbonate aqueous solution and 100 mL of ethyl acetate. Then, 100 mL of water and 100 mL of ethyl acetate were added and stirred, and the mixture was allowed to stand for 5 minutes. The mixture was then separated, and the aqueous layer was extracted three times with 50 mL of ethyl acetate. The organic layers were combined, washed once with 100 mL of water, once with 10 mL of saturated brine, and twice with 5 mL of saturated brine. After drying with magnesium sulfate and filtering the solid components, the solid was distilled off at 40 °C to obtain a yellow solid.

[0424] The obtained yellow solid was dissolved in 6.5 mL of acetone, and the acetone solution was added to 300 mL of water. The precipitated solid was collected by filtration, washed with a small amount of isopropanol (IPA), and dried under reduced pressure at 50 °C for 20 hours to obtain 5.71 parts by mass of the yellow solid. 1 H-NMR analysis confirmed that it was the maleimide compound (TMDM) shown in formula (21).

[0425] TMDM 1 The H-NMR attribution is shown below. Additionally, 1 H-NMR diagram is shown in Figure 2 .

[0426] 1 H-NMR (300MHz, DMSO-d6) δ (ppm): 7.19 (m, 11H, ArH, -CH=CH-), 2.42 (m, 2H, -CH2-), 1.66 (d, 3H, -CH3), 1.32 (d, 3H, -CH3), 1.00 (d, 3H, -CH3)

[0427] [Synthesis of the compound shown in formula (6)]

[0428] [Synthesis example 2]

[0429] The compound shown in formula (6) (also known as compound (A-1)) is synthesized as follows.

[0430] Add 12.52 g (50 mmol) of bis(trimethylolpropane) (manufactured by Tokyo Chemical Industry Co., Ltd.), 41.62 g (210 mmol) of cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., H-TMAn-S (trade name)), 6.10 g (50 mmol) of 4-dimethylaminopyridine, 22.26 g of triethylamine and 150 g of dichloromethane to a 200 mL flask, and stir at room temperature (25 °C) for 9 hours.

[0431] 200 mL of 10% hydrochloric acid and 200 mL of methyl ethyl ketone were added to the reaction solution, which was then transferred to a separatory funnel. The solution was washed twice with 100 mL of 10% hydrochloric acid and twice with 150 mL of saturated saline solution. The solution was dried over magnesium sulfate, and the solvent was removed by distillation. The solution was then dried under vacuum at 120 °C to obtain 44.00 g of a white solid. The obtained white solid was subjected to… 1 H-NMR determination confirmed that it was the compound (A-1) shown in formula (6).

[0432] The following shows the compound (A-1) 1 The assignment of H-NMR. Additionally, 1 The H-NMR spectrum is shown in Figure 3 .

[0433] 1 H-NMR (500MHz, DMSO-d6) δ (ppm): 12.25 (s, 8H, -COOH), 3.85 (s, 8H), 3.20 (s, 4H), 3.08 (s, 4H), 2.58 (m, 4H), 2.26 (t, 4H), 2.09 (m, 8H), 1.74 (m, 8H), 1.60 (m, 4H), 1.33 (m, 4H), 1.15 (m, 4H), 0.78 (t, 6H)

[0434] In addition, the content of compound (A-1) in the aforementioned reaction solution was determined by the following method.

[0435] Add 50 mg of reaction solution to 4500 mg of THF (tetrahydrofuran) to prepare the sample solution. Perform GPC analysis on this solution under the following conditions. Calculate the peak area based on the obtained elution curve, and determine the GPC area percentage (content) of each component in the reaction solution. It should be noted that the peak area is calculated from the area between the elution curve and the baseline. For incompletely separated peaks, vertical segmentation is used for calculation.

[0436] (Measurement conditions)

[0437] Measuring instrument: Prominence (trade name) manufactured by Shimadzu Corporation.

[0438] Pillars: KF-801 (trade name), KF-802 (trade name), KF-803 (trade name), and KF-804 (trade name) manufactured by Showa Denko Corporation.

[0439] Flow rate: 1 mL / min

[0440] Column temperature: 40℃

[0441] Detector: RI (Refractive Index) detector

[0442] According to the GPC determination results, the content of compound (A-1) in the reaction solution was 88%.

[0443] [Example 1]

[0444] (Preparation of resin compositions and resin sheets)

[0445] The following compounds were prepared: 6.75 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A); 0.36 parts by mass of cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) as compound (B); 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14) manufactured by Nippon Kayaku Co., Ltd.) as maleimide compound (C); 25 parts by mass of BCPH01 (trade name, compound shown in formula (22) manufactured by Gunei Chemical Industry Co., Ltd.) as maleimide compound (C); 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C); and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). A mixture of 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), with the addition of 213.3 parts by weight of methyl ethyl ketone (MEK), was heated on a hot plate at 90°C to obtain a varnish (resin composition). This varnish was then dropped onto a 25 μm thick PET film (UNIPEEL TR1-25 (trade name) manufactured by UNITIKA) and spin-coated (500 rpm for 10 seconds, then 1000 rpm for 30 seconds) to form a coating. The resulting coating was dried at 90°C for 5 minutes to obtain a resin sheet with a resin layer thickness of 5 μm, supported by a PET film.

[0446] (Evaluation of the creation of layered bodies)

[0447] The obtained resin sheet was placed on the oxide film side of a silicon wafer (Advantech, 625 μm thick, with 1 μm oxide film) with the resin surface facing it. A vacuum laminator (NIKKO MATERIALS) was used to evacuate the wafer for 30 seconds (below 5.0 hPa). Then, a pressure of 10 kgf / cm² was applied. 2 The material is laminated at 100°C for 30 seconds. Then, it is laminated under a pressure of 7 kgf / cm². 2 The silicon wafer, resin layer and support are laminated at 100°C for 60 seconds to obtain an evaluation laminate.

[0448] [Example 2]

[0449] 4.50 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A), 1.44 parts by mass of cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) as compound (B), 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14) manufactured by Nippon Kayaku Co., Ltd.) as maleimide compound (C), 25 parts by mass of BCPH01 (trade name, compound shown in formula (22) manufactured by Gunei Chemical Industry Co., Ltd.) as maleimide compound (C), 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0450] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0451] [Example 3]

[0452] 5.25 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A), 1.08 parts by mass of cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) as compound (B), and 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14) manufactured by Nippon Kayaku Co., Ltd.) as maleimide compound (C). 25 parts by mass of BCPH01 (trade name, compound shown in formula (22)) manufactured by Gunei Chemical Industry Co., Ltd. as maleimide compound (C), 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C), 5.00 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure (registered trademark) OXE02 (trade name) manufactured by BASF JAPAN Co., Ltd.) as photocuring initiator (D) and 3.00 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by mass of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate heated to 90°C to obtain a varnish (resin composition).

[0453] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0454] [Example 4]

[0455] The following compounds were prepared: 6.85 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A); 2.86 parts by mass of KAYARAD (registered trademark) ZCR-6007H (trade name, a mixture containing compound (A1) and any one or more of compounds (A2) to (A5)) as compound (B); 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14)) manufactured by Nippon Kayaku Co., Ltd. as maleimide compound (C); 25 parts by mass of BCPH01 (trade name, compound shown in formula (22)) manufactured by Gunei Chemical Industry Co., Ltd. as maleimide compound (C); 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C); and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0456] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0457] [Example 5]

[0458] The following compounds were used: 5.54 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A); 8.59 parts by mass of KAYARAD (registered trademark) ZCR-6007H (trade name, a mixture containing compound (A1) and any one or more of compounds (A2) to (A5)) as compound (B); 60 parts by mass of MIZ-001 manufactured by Nippon Kayaku Co., Ltd. (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14)) as maleimide compound (C); 25 parts by mass of BCPH01 manufactured by Gunei Chemical Industry Co., Ltd. (trade name, compound shown in formula (22)) as maleimide compound (C); 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C); and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0459] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0460] [Comparative Example 1]

[0461] 7.50 parts by mass of compound (A-1) obtained in Synthesis Example 2 as compound (A), 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14)) manufactured by Nippon Kayaku Co., Ltd. as maleimide compound (C), 25 parts by mass of BCPH01 (trade name, compound shown in formula (22)) manufactured by Gunei Chemical Industry Co., Ltd. as maleimide compound (C), 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0462] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0463] [Comparative Example 2]

[0464] The following compounds were used as compound (B): 3.58 parts by mass of cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.); 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14) manufactured by Nippon Kayaku Co., Ltd.) as maleimide compound (C); 25 parts by mass of BCPH01 (trade name, compound shown in formula (22) manufactured by Gunei Chemical Industry Co., Ltd.) as maleimide compound (C); 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C); and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by BV, 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0465] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0466] [Comparative Example 3]

[0467] The following compounds were used as compound (B): 31.03 parts by mass of KAYARAD (registered trademark) ZCR-6007H (trade name, a mixture containing compound (A1) and any one or more of compounds (A2) to (A5); 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14)) manufactured by Nippon Kayaku Co., Ltd. as maleimide compound (C); 25 parts by mass of BCPH01 (trade name, compound shown in formula (22)) manufactured by Gunei Chemical Industry Co., Ltd. as maleimide compound (C); 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C); and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as photocuring initiator (D). 3.70 parts by weight of Omnirad 819 (trade name) manufactured by Resins B.V., 1.30 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (Irgacure OXE02 (trade name) manufactured by BASF JAPAN), and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate to 90°C to obtain a varnish (resin composition).

[0468] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0469] [Comparative Example 4]

[0470] 60 parts by mass of MIZ-001 (trade name, mass-average molecular weight (Mw): 3000, compound shown in formula (14)) manufactured by Nippon Kayaku Co., Ltd. as maleimide compound (C), 25 parts by mass of BCPH01 (trade name, compound shown in formula (22)) manufactured by Gunei Chemical Industry Co., Ltd. as maleimide compound (C), 15 parts by mass of TMDM (compound shown in formula (21) obtained in Synthesis Example 1) as maleimide compound (C), 3.70 parts by mass of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV Co., Ltd.) as photocuring initiator (D), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime) (BASF) 1.30 parts by weight of Irgacure (registered trademark) OXE02 (trade name) manufactured by JAPAN Corporation and 3.00 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and 213.3 parts by weight of methyl ethyl ketone (MEK) were added. The mixture was heated on a heating plate at 90°C to obtain a varnish (resin composition).

[0471] Using the obtained varnish, resin sheets and evaluation laminates were obtained using the same method as in Example 1.

[0472] 〔evaluate〕

[0473] The resin sheets and evaluation laminates obtained in the examples and comparative examples were measured and evaluated using the methods described below. The results are shown in Table 1.

[0474] <Photocurability>

[0475] Using a Photo-DSC (TA Instruments Japan DSC-2500) equipped with a light source capable of irradiating active energy rays containing wavelengths of 200–600 nm (U-VIX Omnicure S2000), the obtained resin sheet was irradiated with active energy rays containing wavelengths of 200–600 nm at an illuminance of 30 mW for an exposure time of 3.5 minutes, and a curve was obtained with time (seconds) on the horizontal axis and heat flux (mW) on the vertical axis.

[0476] In the resulting curve, the peak area at which a horizontal line is drawn from the end of the curve is set as the enthalpy (J / g). Curing properties are evaluated according to the following criteria.

[0477] “AA”: Enthalpy is 1 (J / g) or higher.

[0478] “CC”: Enthalpy less than 1 (J / g).

[0479] It should be noted that an enthalpy of 1 (J / g) or higher means that the resin can be fully cured by exposure at a specified wavelength.

[0480] <Peelability after development>

[0481] For the resulting evaluation laminate, a light source capable of irradiating active energy rays containing wavelengths of 200–600 nm (MIKASA MA-20 (trade name)) was used, with an illuminance of 18 mW and an irradiation dose of 200 mJ / cm² from the support. 2 Irradiation was performed using active energy rays with wavelengths of 200–600 nm. Subsequently, the silicon wafer was heated at 90°C for 60 seconds using a heating plate heated to 90°C. Afterward, it was cooled to room temperature. Then, the support (PET film) was peeled off and the wafer was oscillated for 180 seconds in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution (developer, manufactured by TOKUYAMA) at 35°C.

[0482] The peelability after development is evaluated visually according to the following criteria.

[0483] “AA”: No peeling of the exposed resin layer occurred after development.

[0484] "CC": This refers to the peeling of the exposed resin layer that occurs after development.

[0485] <Alkali-developable properties>

[0486] For the resulting evaluation laminate, a light source capable of irradiating active energy rays containing wavelengths of 200–600 nm (MIKASA MA-20 (trade name)) was used, separated by a chromium mask with through-hole patterns (through-hole diameters of 30 μm, 40 μm, 50 μm, and 60 μm), and the light was emitted from the support at an illuminance of 18 mW and an irradiation dose of 200 mJ / cm². 2 Irradiation was performed using active energy rays with wavelengths ranging from 200 to 600 nm. Subsequently, the silicon wafer was heated at 90°C for 60 seconds using a heating plate heated to 90°C. It was then cooled to room temperature. The support (PET film) was then peeled off, and the wafer was agitated for 180 seconds in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution (developer, manufactured by TOKUYAMA) at 35°C. The via pattern was then observed using an optical microscope, and alkaline developability was evaluated according to the following criteria.

[0487] “AA”: After development, it can form through holes with a diameter of less than 30μm.

[0488] “BB”: After development, it can form through-holes larger than φ30μm and smaller than 60μm.

[0489] "CC": After development, it is impossible to form a through hole smaller than φ60μm.

[0490] It should be noted that in Comparative Example 3, the resin sheet was peeled off from the silicon wafer after development, therefore, the alkaline developability could not be measured.

[0491] [Table 1]

[0492]

[0493] As clearly shown in Table 2, according to this embodiment, even when exposed to any light source containing active energy rays with wavelengths of 200–600 nm, good photosensitivity and photocuring are achievable. Furthermore, according to this embodiment, cured products with excellent alkali developability can be obtained.

[0494] This application claims priority to Japanese Patent Application No. 2021-099134, filed with the Japan Patent Office on June 15, 2021, the contents of which are incorporated herein by reference.

[0495] Industrial availability

[0496] The resin composition of this embodiment does not hinder the photocuring reaction during the exposure process of manufacturing multilayer printed circuit boards, and can impart excellent alkaline developability during the development process. Therefore, it is useful in industry and can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed circuit boards, etc.), solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, through-hole resins, and component embedding resins, etc.

Claims

1. A resin composition comprising: The compound (A) shown in formula (1) below; Compounds (B) containing one or more carboxyl groups, other than compound (A) shown in formula (1) below; and Maleimide compound (C). The compound (B) containing one or more carboxyl groups is at least one selected from the group consisting of anhydrides of fully hydrogenated aromatic polycarboxylic acids, anhydrides of partially hydrogenated aromatic polycarboxylic acids, and acid-modified epoxy (meth)acrylates. The maleimide compound (C) comprises a bismaleimide compound (C1), which comprises a structural unit as shown in formula (4) and maleimide groups located at both ends of the molecular chain. The content of compound (A) represented by formula (1) is 0.1 to 30 parts by mass relative to 100 parts by mass of the resin solids in the resin composition. The content of the compound (B) containing one or more carboxyl groups is 0.05 to 30 parts by weight relative to 100 parts by weight of the resin solids in the resin composition. The total content of the maleimide compound (C) is 10 to 100 parts by weight relative to 100 parts by weight of the resin solids in the resin composition. In formula (1), R1 independently represents each of the groups or hydrogen atoms shown in formula (2) below, and R2 independently represents each of the hydrogen atoms, or straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein, At least one R1 is a group represented by the following formula (2), In equation (2), Indicates atomic bond, In formula (4), R3 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms; R4 represents a straight-chain alkylene or branched alkylene with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms; R5 each independently represents a hydrogen atom, a straight-chain alkylene or branched alkyl with 1 to 16 carbon atoms, or a straight-chain alkenyl or branched alkenyl with 2 to 16 carbon atoms; and n1 each independently represents an integer from 1 to 10.

2. The resin composition according to claim 1, wherein, In formula (1), at least one of R1 is a group represented by formula (3) below. In equation (3), It represents an atomic bond.

3. The resin composition according to claim 1, further comprising a photocuring initiator (D).

4. A resin sheet having a support body and a resin layer disposed on one or both sides of the support body, The resin layer comprises the resin composition of claim 1.

5. The resin sheet according to claim 4, wherein, The thickness of the resin layer is 1~50μm.

6. A multilayer printed circuit board having an insulating layer and conductor layers formed on one or both sides of the insulating layer, The insulating layer comprises the resin composition of claim 1.

7. A semiconductor device comprising the resin composition of claim 1.

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