Compound and method for producing same, resin composition, resin sheet, multilayer printed wiring board, and semiconductor device

Abstract

A compound (A) according to the present invention is represented by formula (1).　(1): R1O―R2―OR1. (In formula (1), R1s each independently represent a group represented by formula (2) or a hydrogen atom, and R2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. At least one R1 is a group represented by formula (2).) (In formula (2), -* indicates a bond.)

Description

[Technical field]

[0001] The present invention relates to a compound and a method for producing the same, a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device. [Background technology]

[0002] Due to the miniaturization and high density of multilayer printed wiring boards, there has been active research into making the laminates used in multilayer printed wiring boards thinner. As the thickness is reduced, the insulating layer is also required to be thinner, and a resin sheet that does not contain glass cloth is required. Thermosetting resins are the mainstream resin composition used for the insulating layer, and holes to obtain electrical continuity between insulating layers are generally made by laser processing.

[0003] On the other hand, the problem with drilling holes by laser processing is that the more holes there are in a high-density substrate, the longer the processing time becomes. Therefore, in recent years, there has been a demand for a resin sheet that can be drilled in one step by using a resin composition in which the exposed parts are cured (exposure step) by irradiation with light or the like and the unexposed parts can be removed (development step).

[0004] As an exposure method, a method of exposure through a photomask using a mercury lamp as a light source is used, and a material that can be suitably exposed with this mercury lamp light source is required. In this exposure method using a mercury lamp as a light source, ghi crosstalk (g-line wavelength 436 nm, h-line wavelength 405 nm, i-line wavelength 365 nm) and the like are used, and a general-purpose photocuring initiator can be selected. In addition, in recent years, as an exposure method, a direct writing exposure method in which a photosensitive resin composition layer is directly written without a photomask based on digital data of a pattern is also being introduced. This direct writing exposure method has better alignment accuracy than the exposure method using a photomask, and a high-definition pattern can be obtained, so it is being introduced particularly in substrates that require high-density wiring formation. The light source uses monochromatic light such as a laser, and in particular, a light source with a wavelength of 405 nm (h-line) is used in a DMD (Digital Micro mirror Device) type device that can form a high-definition resist pattern.

[0005] As a developing method, alkaline development is used because it allows a highly precise pattern to be obtained.

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

[0007] Patent Document 2 also describes a resin composition containing a polycarboxyl group-containing compound obtained by reacting bismaleimide with a monoamine and then reacting it with an acid anhydride, and a curable resin such as an epoxy resin. Patent Document 2 also describes a polycarboxyl group-containing compound that can give a cured product having alkali developability. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] WO2018 / 56466A1 [Patent Document 2] JP2015-229734A Summary of the Invention [Problem to be solved by the invention]

[0009] However, in Patent Document 1, a bismaleimide compound is used as a curable resin, but since maleimide compounds usually have poor light transmittance, when a maleimide compound is included, light does not reach the photocuring initiator sufficiently, and the photocuring initiator does not easily generate radicals, and its reactivity is very low. Therefore, in Patent Document 1, the maleimide compound is cured by additional heating before development, but since heating is involved, a high-definition resist pattern cannot be obtained. In addition, the resin composition described in Patent Document 1 does not have sufficient alkaline developability to begin with, so that unexposed resin composition remains even after development. Therefore, from this point of view, Patent Document 1 does not obtain a high-definition resist pattern, and cannot be used for manufacturing high-density printed wiring boards.

[0010] In addition, the polycarboxyl group-containing compound described in Patent Document 2 requires a complicated process because it is necessary to react bismaleimide with a monoamine and then react with an acid anhydride. In addition, since an aromatic amine compound is used as the monoamine, this polycarboxyl group-containing compound contains an amide group having an aromatic ring in its structure. Therefore, this polycarboxyl group-containing compound has poor light transmittance and inhibits the photocuring reaction, so it is actually difficult to use it in a photosensitive resin composition.

[0011] Therefore, the present invention has been made in consideration of the problems of the conventional technology, and an object of the present invention is to provide a compound that, when used in the production of a multilayer printed wiring board, does not inhibit a photocuring reaction in an exposure step and can impart excellent alkaline developability in a development step, as well as said compound, a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device each containing said compound. [Means for solving the problem]

[0012] Means for Solving the Problems The present inventors have conducted intensive research and have found that by using a compound containing a specific carboxyl group in the exposure step and development step in the production of a multilayer printed wiring board, a cured product can be suitably obtained without inhibiting the photocuring reaction, and excellent alkaline developability can be imparted to a resin composition, thereby completing the present invention.

[0013] That is, the present invention includes the following. [1] Compound (A) represented by the following formula (1): A compound (A) represented by the following formula (1):

[0014] [ka]

[0015] (In formula (1), each R1 independently represents a group represented by the following formula (2) or a hydrogen atom, and R2 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms, with the proviso that at least one R1 is a group represented by the following formula (2).)

[0016] [ka]

[0017] (In formula (2), -* represents a bond.)

[0018] [2] The compound (A) according to [1], wherein at least one of R1 is a group represented by the following formula (3):

[0019] [ka]

[0020] (In formula (3), -* represents a bond.)

[0021] [3] A method for producing compound (A) according to [1] or [2], comprising a step of reacting an alcohol compound represented by the following formula (4) with an acid anhydride represented by the following formula (5):

[0022] [ka]

[0023] (In the formula (4), R3 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms).

[0024] [ka]

[0025] [4] The method according to [3], wherein the acid anhydride represented by the formula (5) includes an acid anhydride represented by the following formula (6):

[0026] [ka]

[0027] [5] A resin composition comprising the compound (A) according to [1] or [2]. [6] The resin composition according to [5], further comprising a bismaleimide compound (B) containing a structural unit represented by the following formula (7) and maleimide groups at both ends of the molecular chain:

[0028] [ka]

[0029] (In formula (7), R4 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R5 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. Each R6 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Each n1 independently represents an integer of 1 to 10.)

[0030] [7] The resin composition according to [5] or [6], further comprising at least one maleimide compound (C) selected from the group consisting of a compound represented by the following formula (8), a compound represented by the following formula (9), a compound represented by the following formula (10), a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13).

[0031] [ka]

[0032] (In the formula (8), R7, R8, and R9 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent.)

[0033] [ka]

[0034] (In formula (9), R 10 , R 11 , and R 12 each independently represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. n2 represents an integer of 1 to 10.

[0035] [ka]

[0036] (In formula (10), R 13 each independently represents a hydrogen atom, a methyl group, or an ethyl group; R 14 each independently represents a hydrogen atom or a methyl group.

[0037] [ka]

[0038] (In formula (11), R 15 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 10.

[0039] [ka]

[0040] (In formula (12), R 16 each independently represents a hydrogen atom, a methyl group, or an ethyl group.

[0041] [ka]

[0042] (In formula (13), R 17 each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 to 10.

[0043] [8] The resin composition according to any one of [5] to [7], further comprising a photocuring initiator (D).

[0044] [9] The resin composition according to [8], wherein the photocuring initiator (D) contains a compound represented by the following formula (14):

[0045] [ka]

[0046] (In formula (14), R18 each independently represents a group represented by the following formula (15) or a phenyl group.

[0047] [ka]

[0048] (In formula (15), -* represents a bond, and R 19 each independently represents a hydrogen atom or a methyl group.

[0049]

[10] A resin sheet comprising a support and a resin layer disposed on one or both sides of the support, the resin layer comprising the resin composition according to any one of [5] to [9].

[11] The resin sheet according to

[10] , wherein the resin layer has a thickness of 1 to 50 μm.

[12] A multilayer printed wiring board comprising an insulating layer and a conductor layer formed on one or both sides of the insulating layer, the conductor layer comprising the resin composition according to any one of [5] to [9].

[13] A semiconductor device comprising the resin composition according to any one of [5] to [9]. Effect of the Invention

[0050] According to the present invention, by using a compound containing a specific carboxyl group in the exposure step and development step in the production of a multilayer printed wiring board, it is possible to provide a compound that can suitably obtain a cured product without inhibiting the photocuring reaction and can impart excellent alkaline developability to a resin composition, as well as the compound, a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device each containing the compound. [Brief description of the drawings]

[0051] [Figure 1] FIG. 1 is a 1H-NMR chart of the amide acid compound (MA-TMDA). [Diagram 2] FIG. 2 is a 1H-NMR chart of the maleimide compound (TMDM). [Diagram 3]FIG. 3 is a 1H-NMR chart of compound (A-1). [Figure 4] FIG. 4 is a 1H-NMR chart of compound (A-2). [Diagram 5] FIG. 5 is a 1H-NMR chart of compound (A-3). [Figure 6] 1 is a photograph of the resin sheet obtained in Example 4 and Comparative Example 1 after alkali development using active energy rays having a wavelength of 405 nm (h-rays). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0052] Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out with appropriate modifications within the scope of its gist.

[0053] In this specification, "(meth)acryloxy" means both "acryloxy" and the corresponding "methacryloxy", and "(meth)acrylic" means both "acrylic" and the corresponding "methacrylic". In addition, in this embodiment, "resin solid content" or "resin solid content in a resin composition" refers to components in a resin composition excluding compound (A), photocuring initiator (D), additives, solvents, and fillers, unless otherwise specified, and "100 parts by mass of resin solid content" refers to the total of components in a resin composition excluding compound (A), photocuring initiator (D), additives, solvents, and fillers being 100 parts by mass.

[0054] The compound (A) of this embodiment will be described.

[0055] [Compound (A)] The compound (A) (also referred to as component (A)) of this embodiment is represented by formula (1).

[0056] [ka]

[0057] In formula (1), each R1 independently represents a group represented by formula (2) or a hydrogen atom, and R2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms, provided that at least one R1 is a group represented by formula (2).

[0058] [ka]

[0059] In formula (2), -* represents a bond to the oxygen atom (O) directly bonded to R1 in formula (1).

[0060] In this embodiment, by using the compound (A) in the exposure step and development step in the preparation of a multilayer printed wiring board, a cured product can be obtained suitably without inhibiting the photocuring reaction, and excellent alkaline developability can be imparted to the resin composition in the unexposed area even after exposure. The reason for this is unclear, but the present inventors presume it as follows. That is, in the exposure step in the preparation of a multilayer printed wiring board, the compound (A) does not have a functional group involved in the photocuring reaction in the exposure step, and does not inhibit the photocuring reaction. In addition, the compound (A) does not have a skeleton that inhibits light transmittance, and also has very excellent light transmittance. Therefore, even if the compound (A) is contained, photopolymerization proceeds and a cured product can be suitably obtained. And, since the compound (A) does not participate in the photocuring reaction, it can be present in the resin composition in the unexposed area. Therefore, in the development step, when an alkaline developer flows into the unexposed area, the alkaline component in the alkaline developer and the carboxy group in the compound (A) can suitably form a salt, and the water solubility is improved, so that excellent alkaline developability can be obtained. In addition, it is presumed that the compound (A) can impart excellent alkaline developability because it has a plurality of carboxy groups.

[0061] When an N-methylpyrrolidone solution containing 1% by mass of compound (A) is prepared and the transmittance of the N-methylpyrrolidone solution containing 1% by mass of compound (A) is measured using active energy rays including a wavelength of 365 nm (i-rays), the transmittance is 5% or more. Thus, compound (A) exhibits very excellent light transmittance. Also, when the transmittance of an N-methylpyrrolidone solution containing 1% by mass of compound (A) is measured using active energy rays including a wavelength of 405 nm (h-rays), the transmittance is 5% or more. In this case, too, it exhibits very excellent light transmittance. When compound (A) is used in this way, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct writing exposure method, for example, a photoradical reaction of maleimide occurs efficiently even when active energy rays including a wavelength of 405 nm (h-rays) are used. The transmittance at a wavelength of 365 nm (i-line) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order, since a resin composition having superior photocurability can be obtained. The transmittance at a wavelength of 405 nm (h-line) is preferably in the range of 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order, since a resin composition having superior photocurability can be obtained. The upper limit of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less.

[0062] In the compound (A), in formula (1), R1 each independently represents a group represented by formula (2) or a hydrogen atom. Since R1 can impart better alkaline developability, it is preferable that two R1 are groups represented by formula (2). In the group represented by formula (2), when the position of the carbonyl group is the 1st position relative to the cyclohexane ring, as long as a carboxyl group is bonded to the 2nd position relative to the carbonyl group, another carboxyl group may be bonded to any of the 3rd to 6th positions on the cyclohexane ring. In addition, in the group represented by formula (2), the carbonyl group bonded to the cyclohexane ring and the two carboxyl groups have a three-dimensional structure, so that the compound (A) exists as a cis isomer, a trans isomer, and a mixture of the cis isomer and the trans isomer. That is, the compound (A) may be a single type, or a mixture containing two or more isomers.

[0063] In formula (1), since R1 can impart better alkaline developability, at least one of R1 is preferably a group represented by formula (3). That is, in the group represented by formula (3), the three-dimensional structure of the carbonyl group bonded to the 1-position of the cyclohexane ring and the carboxyl group at the 2-position is preferably a cis-form. The three-dimensional structure of the other carboxyl group may be a cis-form or a trans-form. Since R1 can impart even better alkaline developability, two R1 are preferably groups represented by formula (3). Although it is not clear that at least one of R1 is a group represented by formula (3), it can impart better alkaline developability, the present inventors presume as follows. That is, when the carbonyl group bonded to the 1-position and the carboxyl group bonded to the 2-position are cis-forms, the carboxyl group at the 2-position and the alkaline component in the alkaline developer can take a three-dimensional structure that easily forms a salt in the resin composition, which is presumed to be because water solubility is improved and the inflow of the alkaline developer into the resin composition is further promoted.

[0064] [ka]

[0065] In formula (3), -* represents a bond to the oxygen atom (O) directly bonded to R1 in formula (1).

[0066] In formula (1), R2 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R2 is preferably a linear or branched alkylene group from the viewpoint of exhibiting good solubility in a solvent, and more preferably a linear alkylene group from the viewpoints of exhibiting good solubility in a solvent, imparting better alkaline developability, and exhibiting good compatibility with other resins when made into a resin composition.

[0067] The alkylene group preferably has 2 to 14 carbon atoms, and more preferably has 4 to 12 carbon atoms, from the viewpoint of exhibiting better solubility in a solvent. Examples of linear or branched alkylene groups 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, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene. Among these, from the viewpoints of exhibiting good solubility in a solvent, being able to impart more excellent alkaline developability, and exhibiting good compatibility with other resins when made into a resin composition, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and an undecylene group are more preferable.

[0068] The alkenylene group preferably has 2 to 14 carbon atoms, and more preferably has 4 to 12 carbon atoms, from the viewpoint of exhibiting better solubility in a solvent. Examples of linear or branched alkenylene groups include vinylene, 1-methylvinylene, allylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentylene, cyclopentenylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, cyclohexenylene, and dicyclopentadienylene. Among these, 1-hexenylene, 2-hexenylene, 3-hexenylene, cyclohexenylene, and dicyclopentadienylene are more preferred from the viewpoints of exhibiting good solubility in a solvent, imparting better alkaline developability, and exhibiting good compatibility with other resins when used in a resin composition.

[0069] From the viewpoints of exhibiting good solubility in a solvent, being able to impart even better alkaline developability, and exhibiting good compatibility with other resins when made into a resin composition, compound (A) is preferably a compound represented by formula (16), a compound represented by formula (17), or a compound represented by formula (18), and more preferably a compound represented by formula (17) or a compound represented by formula (18).

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [Method for producing compound (A)] Compound (A) can be produced by a known method, for example, by a process including an esterification reaction between an alcohol compound represented by formula (4) and an acid anhydride represented by formula (5) (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride). The acid anhydride represented by formula (5) has a three-dimensional structure with two carbonyl groups and one carboxyl group bonded to the cyclohexane ring, and therefore exists as a cis isomer, a trans isomer, and a mixture of cis isomers and trans isomers. That is, the acid anhydride represented by formula (5) may be a single type, or a mixture containing two or more isomers.

[0074] [ka]

[0075] In formula (4), R3 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. For the linear or branched alkylene group having 1 to 16 carbon atoms or the linear or branched alkenylene group having 2 to 16 carbon atoms, reference can be made to R2 in the above formula (1), including preferred embodiments thereof.

[0076] [ka]

[0077] Examples of the alcohol compound represented by formula (4) include methylene glycol, ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-hexanediol, 1,8-octanediol, 1,2-octanediol, 1,9-octanediol, and 1,2-octanediol. Examples of the dimethyl ether ester include hexanediol, 1,10-decanediol, 1,16-hexadecanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-isoamyl-1,3-propanediol, 2,2-diisobutyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, trans-2-butene-1,4-diol, and cis-2-butene-1,4-diol.

[0078] The acid anhydride represented by formula (5) preferably contains an acid anhydride represented by formula (6) (cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride) because it can impart excellent alkaline developability when a cured product is produced using compound (A). That is, in the acid anhydride represented by formula (6), when the carbonyl groups are located at the 1st and 2nd positions relative to the cyclohexane ring, it is preferable that the three-dimensional structure of the carbonyl group bonded to the 4th position relative to the carbonyl group and the two carbonyl groups is a cis form.

[0079] [ka]

[0080] The esterification reaction can be carried out in a solvent or without a solvent. The solvent is not particularly limited as long as it does not react with the alcohol compound and the acid anhydride. Examples of such solvents include halogenated solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; aromatic group-containing phenol solvents 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 a suitable mixture of two or more. Among these, halogenated solvents, aprotic polar solvents, ketone solvents, and ester solvents are preferred because they can sufficiently dissolve the alcohol compound and the acid anhydride. When a solvent is used, the amount used is usually 20 to 2000 parts by mass per 100 parts by mass of the alcohol compound and the acid anhydride in total.

[0081] The esterification reaction may be carried out without or with a catalyst. When a catalyst is used, examples of the catalyst include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic 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 having an aromatic ring such as aniline, N-methylaniline, N,N-dimethylaniline, and benzylamine; heterocyclic compounds such as pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, and tetrazole; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylamine, and the like. Examples of the catalyst include quaternary ammonium salts such as ammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium 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 octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, and potassium octylate. These catalysts can be used alone or in combination of two or more. Among these, amine compounds, aliphatic amines having an aromatic ring, and heterocyclic compounds are preferred from the viewpoint of good reactivity, and triethylamine and 4-dimethylaminopyridine are more preferred. When a catalyst is used, the amount used is usually 0.001 to 1000 parts by mass per 100 parts by mass of the alcohol compound and the acid anhydride in total.

[0082] Examples of methods for adding the catalyst include a method in which the catalyst is added directly to the alcohol compound and / or the acid anhydride, and a method in which a solution in which the catalyst is dissolved in a soluble solvent or the like is added to the alcohol compound, the acid anhydride, and / or a solvent containing these.

[0083] The reaction temperature in the esterification reaction is not particularly limited depending on the amount of catalyst and the solvent used, but is usually -20 to 150°C. The reaction time is also not particularly limited, but is usually 0.5 to 100 hours. The reaction may be completed in one stage or may be carried out in two or more stages.

[0084] When the target compound (A) is precipitated from the reaction mixture containing the compound (A), it can be isolated by filtration or centrifugation. When the target compound is dissolved in the reaction solvent, it can be precipitated by distilling off the solvent under reduced pressure, adding a suitable poor solvent to the reaction mixture, or discharging the reaction mixture into a poor solvent, and then isolated by filtration or centrifugation. Examples of poor solvents include hydrocarbons such as hexane, heptane, cyclohexane, toluene, and xylene. These solvents can be used alone or in a suitable mixture of two or more. When the isolated compound (A) needs to be further purified, it may be purified by a known method, such as distillation purification, recrystallization, column chromatography, sludge treatment, activated carbon treatment, etc.

[0085] The obtained compound (A) can be identified by a known method such as NMR (nuclear magnetic resonance analysis). The purity of compound (A) can be analyzed, for example, by GPC, liquid chromatography, and IR spectroscopy. Volatile components such as by-products and residual solvents in compound (A) can be quantitatively analyzed, for example, by GPC and gas chromatography. The halogen compounds remaining in compound (A) can be identified, for example, by a liquid chromatograph mass spectrometer. In addition, the halogen compounds remaining in compound (A) can also be quantified by ion chromatography after decomposition by potentiometric titration using a silver nitrate solution or by a combustion method.

[0086] [Resin composition] The resin composition of the present embodiment contains the compound (A) and is suitable for use in the preparation of a multilayer printed wiring board. By using the resin composition, a cured product can be obtained in an appropriate manner without inhibiting the photocuring reaction in the exposure step and development step in the preparation of the multilayer printed wiring board, and excellent alkaline developability can be imparted after exposure.

[0087] In the resin composition, the content of compound (A) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, because this can impart better alkaline developability and enable the resin composition to exhibit good curability without inhibiting the photocuring reaction.

[0088] Furthermore, in the resin composition containing a bismaleimide compound (B) described below and a maleimide compound (C) described below, the content of compound (A) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass in total of the bismaleimide compound (B) described below and the maleimide compound (C) described below, because this can impart better alkaline developability and enable the resin composition to exhibit good curability without inhibiting the photocuring reaction.

[0089] [Bismaleimide compound (B)] The resin composition of the present embodiment preferably further contains a bismaleimide compound (B) (also referred to as component (B)). The bismaleimide compound (B) contains a constitutional unit represented by formula (7) and maleimide groups at both ends of the molecular chain.

[0090] [ka]

[0091] In formula (7), R4 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R5 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. Each R6 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Each n1 independently represents an integer of 1 to 10.

[0092] Usually, maleimide compounds have very low water solubility and no reactivity with the alkaline components in an alkaline developer, making it difficult to obtain alkaline developability. However, the resin composition contains a bismaleimide compound (B) together with the compound (A), and thus has excellent photocurability and very good alkaline developability. The reason for this is unclear, but the present inventors speculate as follows.

[0093] That is, the resin composition contains a compound (A) that does not inhibit the photocuring reaction and can impart excellent alkaline developability to the resin composition. The bismaleimide compound (B) has a relatively long chain and flexible structure, and does not have a structure that causes an interaction with an alkaline component in an alkaline developer. Therefore, the bismaleimide compound (B) can be dissolved in an alkaline developer while maintaining the structure of the compound (A) in the alkaline developer, along with the dissolution of the compound (A) in the alkaline developer. Therefore, in the development process, when the alkaline developer flows into the unexposed area (resin composition), the alkaline component in the alkaline developer and the carboxy group in the compound (A) can quickly and suitably form a salt without being inhibited by the bismaleimide compound (B), and the water solubility is improved. Therefore, it is presumed that the resin composition has excellent alkaline developability.

[0094] The present inventors presume that the reason why the resin composition contains the bismaleimide compound (B) together with the compound (A) and has excellent photocuring reactivity is as follows. Usually, maleimide compounds have poor light transmittance, so when a resin composition contains a maleimide compound, light does not reach the photocuring initiator dispersed in the resin composition sufficiently, and the photocuring initiator does not generate radicals easily. Therefore, the photoradical reaction of maleimide compounds generally does not proceed easily, and even if radical polymerization or dimerization reaction of maleimide alone proceeds, its reactivity is very low. However, since the bismaleimide compound (B) has a structural unit represented by formula (7), i.e., an alicyclic skeleton, it has very good light transmittance. In addition, the compound (A) also has very good light transmittance. Therefore, light reaches the photocuring initiator sufficiently, and the photoradical reaction of maleimide occurs efficiently, and the compound (A) and the bismaleimide compound (B) can be photocured using various active energy rays together with the maleimide compound (C) described below and the photocuring initiator (D) described below, which are mixed as necessary.

[0095] A chloroform solution containing 1% by mass of the bismaleimide compound (B) is prepared, and when the transmittance of the chloroform solution containing 1% by mass of the bismaleimide compound (B) is measured using active energy rays including a wavelength of 365 nm (i-rays), the transmittance is 5% or more, which shows very excellent light transmittance. In addition, when the transmittance of the chloroform solution containing 1% by mass of the bismaleimide compound (B) is measured using active energy rays including a wavelength of 405 nm (h-rays), the transmittance is 5% or more, which shows very excellent light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct writing exposure method, the photoradical reaction of maleimide occurs efficiently even when active energy rays including a wavelength of 405 nm (h-rays) are used. The transmittance at a wavelength of 365 nm (i-rays) is preferably 8% or more, more preferably 10% or more, in terms of showing better light transmittance. The transmittance at a wavelength of 405 nm (h-line) is preferably 8% or more, more preferably 10% or more, from the viewpoint of producing a printed wiring board having a higher density and higher definition wiring formation (pattern). The upper limit of each of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less.

[0096] Usually, photocuring initiators tend to have low absorbance for light in the long wavelength region. For example, when using active energy rays (light rays) including a wavelength of 405 nm (h-rays), this wavelength of light is relatively long, so it is not absorbed by normal photocuring initiators, and polymerization does not proceed unless a photocuring initiator that can appropriately absorb this light and generate radicals is used. Therefore, as the photocuring initiator (D) described later, it is preferable to use a photocuring initiator that has an absorbance of 0.1 or more for light of a wavelength of 405 nm (h-rays) when the absorbance of a chloroform solution containing 0.01 mass% of the photocuring initiator (D) is measured, and that shows very good absorbance.

[0097] As described above, the bismaleimide compound (B) has excellent light transmittance. Therefore, even when active energy rays having a wavelength of, for example, 365 nm or 405 nm are used, the light sufficiently reaches the photocuring initiator, and a radical reaction using radicals generated from the photocuring initiator proceeds, making it possible to photocur even in a composition containing a large amount of the bismaleimide compound (B). The resin composition has excellent alkali developability and photocurability. The cured product has excellent heat resistance, insulation reliability, and thermal stability. Therefore, according to the present embodiment, a protective film and an insulating layer can be suitably formed in a multilayer printed wiring board and a semiconductor device.

[0098] The bismaleimide compound (B) is not particularly limited as long as it exhibits the effects of the present invention, but in terms of obtaining a suitable viscosity and suppressing an increase in the viscosity of the varnish, the mass average molecular weight is preferably 100 to 5000, and more preferably 300 to 4500. In this embodiment, the "mass average molecular weight" means the mass average molecular weight calculated as a polystyrene standard by gel permeation chromatography (GPC).

[0099] Next, the structure of the bismaleimide compound (B) will be described. In the formula (7) of the bismaleimide compound (B), R4 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R4 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoints of obtaining a suitable viscosity and controlling the increase in the viscosity of the varnish.

[0100] The number of carbon atoms in the alkylene group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled. For the linear or branched alkylene group, see R2 in the above formula (1).

[0101] The alkenylene group preferably has 2 to 14 carbon atoms, and more preferably 4 to 12 carbon atoms, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled. For the linear or branched alkenylene group, see R2 in the above formula (1).

[0102] In formula (7), R5 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R5 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoints of obtaining a suitable viscosity and controlling the increase in the viscosity of the varnish.

[0103] The number of carbon atoms in the alkylene group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled. As the linear or branched alkylene group, reference can be made to R2 in the above formula (1).

[0104] The alkenylene group preferably has 2 to 14 carbon atoms, and more preferably 4 to 12 carbon atoms, in that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled. As the linear or branched alkenylene group, reference can be made to R2 in the above formula (1).

[0105] In the formula (7), R4 and R5 may be the same or different, but are preferably the same in terms of facilitating the synthesis of the bismaleimide compound (B).

[0106] In formula (7), R6 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. From the viewpoint of obtaining a suitable viscosity and controlling the increase in the viscosity of the varnish, R6 each independently represents preferably a hydrogen atom, or a linear or branched alkyl group having 1 to 16 carbon atoms, more preferably groups (R6) 1 to 5 of R6 represent a linear or branched alkyl group having 1 to 16 carbon atoms and the remaining groups (R6) represent a hydrogen atom, and further preferably groups (R6) 1 to 3 of R6 represent a linear or branched alkyl group having 1 to 16 carbon atoms and the remaining groups (R6) represent a hydrogen atom.

[0107] The number of carbon atoms in the alkyl group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 1-ethylpropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a tert-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, an n-heptyl group, an n-octyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 2-methylpentan-3-yl group, and an n-nonyl group.

[0108] The number of carbon atoms in the alkenyl group is preferably from 2 to 14, and more preferably from 4 to 12, in that a more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled. Examples of linear or branched alkenyl groups include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl groups.

[0109] In formula (7), n1 each independently represents an integer of 1 to 10.

[0110] The bismaleimide compound (B) has maleimide groups at both ends of the molecular chain. Both ends means both ends of the molecular chain of the bismaleimide compound (B). For example, when the structural unit represented by formula (7) is at the end of the molecular chain of the bismaleimide compound (B), the maleimide group is at the end of the molecular chain of R4, at the end of the molecular chain at the N atom of the maleimide ring, or at both ends. The bismaleimide compound (B) may have maleimide groups in addition to both ends of the molecular chain. The maleimide group is represented by formula (19), and the N atom is bonded to the molecular chain of the bismaleimide compound (B). The maleimide groups bonded to the bismaleimide compound (B) may all be the same or different, but it is preferable that the maleimide groups at both ends of the molecular chain are the same.

[0111] [ka]

[0112] In formula (19), R 20 R each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. 20 From the viewpoint of suitable photocuring, it is preferable that both of the radicals are hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1 to 3, and more preferably 1 or 2, from the viewpoint of suitable photocuring. As the linear or branched alkyl group, reference can be made to R6 above.

[0113] An example of such a bismaleimide compound (B) is a maleimide compound represented by the formula (20). These can be used alone or in a suitable mixture of two or more kinds.

[0114] [ka]

[0115] In formula (20), a represents an integer of 1 to 10. It is preferable that a is an integer of 1 to 6, since a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be better controlled.

[0116] Commercially available bismaleimide compounds (B) may also be used, such as MIZ-001 (trade name, containing the maleimide compound of formula (20)) manufactured by Nippon Kayaku Co., Ltd.

[0117] In the resin composition, the content of the bismaleimide compound (B) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 70 parts by mass, per 100 parts by mass of the resin solid content, from the viewpoints that a cured product containing the bismaleimide compound as a main component can be obtained, photocurability can be improved, and better heat resistance and thermal stability can be obtained.

[0118] Furthermore, in the case where the resin composition contains a bismaleimide compound (B) and a maleimide compound (C) described below, the content of the bismaleimide compound (B) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 70 parts by mass, per 100 parts by mass in total of the bismaleimide compound (B) and the maleimide compound (C) described below, from the viewpoints that a cured product containing the bismaleimide compound as a main component can be obtained, photocurability can be improved, and better heat resistance and thermal stability can be obtained.

[0119] The bismaleimide compound (B) may be used alone or in a suitable mixture of two or more kinds.

[0120] (Method for producing bismaleimide compound (B)) The bismaleimide compound (B) can be produced by a known method. For example, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a monomer containing a diamine such as dimer diamine, and maleic anhydride are subjected to a polyaddition reaction at a temperature of usually about 80 to 250°C, preferably about 100 to 200°C, for usually about 0.5 to 50 hours, preferably about 1 to 20 hours, to obtain a polyaddition product. Thereafter, the polyaddition product is subjected to an imidization reaction, i.e., a dehydration ring-closing reaction, at a temperature of usually about 60 to 120°C, preferably about 80 to 100°C, for usually about 0.1 to 2 hours, preferably about 0.1 to 0.5 hours, to obtain the bismaleimide compound (B).

[0121] Dimer diamine is obtained, for example, by reductive amination reaction of dimer acid, and the amination reaction can be carried out by known methods (for example, the method described in JP-A-9-12712), such as a reduction method using ammonia and a catalyst. Dimer acid is a dibasic acid obtained by dimerization of unsaturated fatty acid by intermolecular polymerization reaction or the like. Although it depends on synthesis conditions and purification conditions, in addition to dimer acid, small amounts of monomer acid, trimer acid, etc. are usually contained. After the reaction, double bonds remain in the obtained molecule, but in this embodiment, dimer acid also includes those in which the double bonds present in the molecule are reduced by a hydrogenation reaction to become saturated dibasic acids. Dimer acid is obtained, for example, by polymerization of unsaturated fatty acid using Lewis acid and Bronsted acid as catalysts. Dimer acid can be produced by known methods (for example, the method described in JP-A-9-12712). Examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinoleic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, osbondoic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, and herring acid. The number of carbon atoms of unsaturated fatty acids is usually 4 to 24, and preferably 14 to 20.

[0122] In the production of the bismaleimide compound (B), it is preferable that the diamine-containing monomer is dissolved or dispersed in a slurry state in an organic solvent in advance in an inert atmosphere such as argon, nitrogen, etc. to prepare a diamine-containing monomer solution. Then, it is preferable that 1,2,4,5-cyclohexanetetracarboxylic dianhydride is added to the diamine-containing monomer solution after being dissolved or dispersed in a slurry state in an organic solvent, or in a solid state. Any bismaleimide compound (B) can be obtained by adjusting the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the total number of moles of the diamine-containing monomer and the maleimide compound.

[0123] Various known solvents can be used in the polyaddition reaction and the imidization reaction. Examples of the solvent 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; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol, and propanol; aromatic group-containing phenols such as phenol and cresol; benzyl alcohols such as ethyl acetate, butyl acetate, and butyl acetate; and methyl alcohols such as ethyl acetate, butyl ... Examples of the solvent include aromatic group-containing alcohols such as ethanol; glycols such as ethylene glycol and propylene glycol, or monoethers or diethers of these glycols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of these monoethers; cyclic ethers such as dioxane and tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; and aprotic polar solvents such as dimethyl sulfoxide. These solvents can be used alone or in combination of two or more as needed.

[0124] In addition, in the imidization reaction, it is preferable to use a catalyst. For example, a tertiary amine and a dehydration catalyst can be used as the catalyst. For the tertiary amine, a heterocyclic tertiary amine is preferable, and for example, pyridine, picoline, quinoline, and isoquinoline can be mentioned. For the dehydration catalyst, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride can be mentioned. The amount of catalyst added is preferably, for example, about 0.5 to 5.0 molar equivalents of the imidizing agent relative to the amide group, and 0.5 to 10.0 molar equivalents of the dehydration catalyst relative to the amide group.

[0125] After the imidization reaction is completed, this solution may be used as a bismaleimide compound (B) solution, or a poor solvent may be added to the reaction solvent to convert the bismaleimide compound (B) into a solid. Examples of poor solvents include water, methyl alcohol, ethyl alcohol, 2-propyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-pentyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, and t-butyl alcohol.

[0126] <Maleimide Compound (C)> The resin composition of the present embodiment preferably further contains a maleimide compound (C) (also referred to as component (C)) other than the bismaleimide compound (B) of the present embodiment. The maleimide compound (C) is at least one selected from the group consisting of a compound represented by formula (8), a compound represented by formula (9), a compound represented by formula (10), a compound represented by formula (11), a compound represented by formula (12), and a compound represented by formula (13). The maleimide compound (C) may be used alone or in an appropriate mixture of two or more. As the maleimide compound (C), from the viewpoints of exhibiting superior heat resistance and thermal stability, good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins, the compound represented by formula (8), the compound represented by formula (9), and the compound represented by formula (10) are preferred, and the compound represented by formula (8) and the compound represented by formula (9) are more preferred.

[0127] As described above, the photoradical reactivity of the maleimide compound is usually very low. However, as described above, the bismaleimide compound (B) has very good light transmittance. In addition, since the compound (A) also has very good light transmittance, by using the bismaleimide compound (A) together with the compound (A), the maleimide compound (C), and the photocuring initiator (D) described below that is mixed as necessary, light can reach the photocuring initiator sufficiently, and the photoradical reaction of the maleimide can efficiently occur, allowing photocuring using various active energy rays.

[0128] Since the compound (A) and the bismaleimide compound (B) have excellent light transmittance, even when an active energy ray having a wavelength including 365 nm or an active energy ray having a wavelength including 405 nm is used, the light sufficiently reaches the photocuring initiator, and a radical reaction using radicals generated from the photocuring initiator proceeds, making it possible to photocur even in a composition containing the maleimide compound (C). The resin composition has excellent alkali developability and photocurability, and the resulting cured product has excellent heat resistance, insulating reliability, and thermal stability, making it suitable for forming protective films and insulating layers.

[0129] Next, the compounds represented by formulae (8) to (13) contained in the maleimide compound (C) will be described.

[0130] (Compound represented by formula (8)) The compound represented by formula (8) is the following compound.

[0131] [ka]

[0132] In formula (8), R7, R8, and R9 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms, which may have a substituent, include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, and a heptyl group. The hydrogen atoms in these alkyl groups may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, and a cyano group. Among these alkyl groups, from the viewpoints of being more excellent in photocurability, heat resistance, and thermal stability, and of exhibiting good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group are preferred, a methyl group, an ethyl group, and an isopropyl group are more preferred, and a methyl group is even more preferred.

[0133] As the compound represented by formula (8), from the viewpoint of exhibiting even better photocurability, heat resistance, thermal stability, solubility in solvents, low melting point, low water absorption, and compatibility with other resins, a compound represented by formula (21) (also referred to as TMDM in this embodiment) is even more preferable.

[0134] [ka]

[0135] (Compound represented by formula (9)) The compound represented by formula (9) is the following compound.

[0136] [ka]

[0137] In formula (9), R 10 , R 11 , and R 12 each independently represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. n2 represents an integer of 1 to 10. As the linear or branched alkyl group having 1 to 6 carbon atoms, reference can be made to R6 in the above formula (7). As the alkyl group, from the viewpoints of exhibiting good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferable, and a methyl group is more preferable. Also, R 10 , R 11 , and R 12 In order to exhibit better solubility in a solvent, R9 and R 12 is a linear or branched alkyl group having 1 to 6 carbon atoms, and R 11 is preferably a hydrogen atom. The preferred alkyl groups are as described above. n2 is preferably an integer from 1 to 10, and more preferably an integer from 1 to 6, from the viewpoints of excellent solubility in solvents, obtaining a more suitable viscosity, and enabling better control of the increase in viscosity of the varnish.

[0138] The compound represented by formula (9) may be a commercially available product, and examples thereof include BCPH13 (product name) manufactured by Gun-ei Chemical Industry Co., Ltd., represented by formula (22), BCPH01 (product name) manufactured by Gun-ei Chemical Industry Co., Ltd., and BMCX426 (product name) manufactured by Gun-ei Chemical Industry Co., Ltd., represented by formula (23).

[0139] [ka]

[0140] In formula (22), n 21 is an integer from 1 to 5.

[0141] [ka]

[0142] In formula (23), n 22 is an integer from 1 to 10.

[0143] (Compound represented by formula (10)) The compound represented by formula (10) is the following compound.

[0144] [ka]

[0145] In formula (10), R 13 each independently represents a hydrogen atom, a methyl group, or an ethyl group; R 14 each independently represents a hydrogen atom or a methyl group. R 13 From the viewpoints of exhibiting good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, the alkyl group is preferably a methyl group or an ethyl group. R 14 From the viewpoint of exhibiting good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, a hydrogen atom is preferable.

[0146] As the maleimide compound represented by formula (10), a commercially available product may be used, and an example thereof is BMI-70 (product name) manufactured by K.I. Chemicals Co., Ltd., represented by formula (24).

[0147] [ka]

[0148] (Compound represented by formula (11)) The compound represented by formula (11) is the following compound.

[0149] [ka]

[0150] In formula (11), R 15 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 10. As the maleimide compound represented by formula (11), a commercially available product may be used, and an example thereof is MIR-3000 (product name) manufactured by Nippon Kayaku Co., Ltd., represented by formula (25).

[0151] [ka]

[0152] In formula (25), n 31 is an integer between 1 and 10.

[0153] (Compound represented by formula (12)) The compound represented by formula (12) is the following compound.

[0154] [ka]

[0155] In formula (12), R 16 each independently represents a hydrogen atom, a methyl group, or an ethyl group. R 16 From the viewpoints of exhibiting good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, the alkyl group is preferably a methyl group or an ethyl group. As the maleimide compound represented by formula (12), a commercially available product may be used, for example, BMI-80 (trade name) represented by formula (26) manufactured by K.I. Chemicals Co., Ltd.

[0156] [ka]

[0157] (Compound represented by formula (13)) The compound represented by formula (13) is the following compound.

[0158] [ka]

[0159] In formula (13), R 17 each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 to 10. R 17 From the viewpoint of exhibiting good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, a hydrogen atom is preferred. It is more preferable that n4 is an integer of 1 to 5, from the viewpoints of excellent solubility in solvents, obtaining a more suitable viscosity, and enabling better control of the increase in the viscosity of the varnish.

[0160] As the maleimide compound represented by formula (13), commercially available products may be used, and examples thereof include BMI-2300 (product name) represented by formula (27) manufactured by Daiwa Chemical Industry Co., Ltd.

[0161] [ka]

[0162] In formula (27), n 41 is an integer from 1 to 5.

[0163] In the resin composition, the content of the maleimide compound (C) is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the resin solid content, from the viewpoint of obtaining better heat resistance and thermal stability.

[0164] Furthermore, in the case where the resin composition contains the bismaleimide compound (B) and the maleimide compound (C), the content of the maleimide compound (C) is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C), from the viewpoint of obtaining better heat resistance and thermal stability.

[0165] [Photocuring initiator (D)] The resin composition of the present embodiment preferably further contains a photocuring initiator (D) (also referred to as component (D)). The photocuring initiator (D) is not particularly limited, and any known initiator generally used in the field of photocurable resin compositions can be used. The photocuring initiator (D) is used to photocure the compound (A) together with the bismaleimide compound (B) and the maleimide compound (C) that are blended as necessary, using various active energy rays.

[0166] Examples of the photocuring initiator (D) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate; phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide, and bisbenzoyl-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2 ... Acetophenones such as 2-ethyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; acetophenone dimethyl ketals such as ketals and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; radical-type photocuring initiators such as oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Examples of the cationic photopolymerization initiator include 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-based initiators; borate-based initiators; and other photoacid generators.

[0167] As the photocuring initiator (D), commercially available products can be used. For example, Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) TPO-G (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 100 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 120 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 10 ... Examples of such an agent include Omnirad (registered trademark) 784 (product name) manufactured by BV, Irgacure (registered trademark) OXE01 (product name) manufactured by BASF Japan Ltd., Irgacure (registered trademark) OXE02 (product name) manufactured by BASF Japan Ltd., Irgacure (registered trademark) OXE03 (product name) manufactured by BASF Japan Ltd., and Irgacure (registered trademark) OXE04 (product name) manufactured by BASF Japan Ltd. These photocuring initiators (D) can be used alone or in a suitable mixture of two or more.

[0168] A chloroform solution containing 0.01% by mass of the photocuring initiator (D) is prepared, and when the absorbance of the chloroform solution containing 0.01% by mass of the photocuring initiator (D) is measured using active energy rays including a wavelength of 365 nm (i-rays), the absorbance is preferably 0.1 or more, and this photocuring initiator (D) shows very excellent absorbance. When the absorbance of the chloroform solution containing 0.01% by mass of the photocuring initiator (D) is measured using active energy rays including a wavelength of 405 nm (h-rays), the absorbance is preferably 0.1 or more, and in this case, it also shows very excellent absorbance. When such a photocuring initiator (D) is used, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct writing exposure method, a photoradical reaction of maleimide occurs efficiently even when active energy rays including a wavelength of 405 nm (h-rays) are used. In addition, the absorbance at a wavelength of 365 nm (i-line) is more preferably 0.15 or more since a resin composition having better photocurability can be obtained. In addition, the absorbance at a wavelength of 405 nm (h-line) is more preferably 0.15 or more since a resin composition having better photocurability can be obtained. In addition, the upper limit of each of the absorbance at a wavelength of 365 (i-line) and the absorbance at a wavelength of 405 nm (h-line) is, for example, 99.9 or less.

[0169] As such a photocuring initiator (D), a compound represented by formula (14) is preferable.

[0170] [ka]

[0171] In formula (14), R 18 each independently represents a substituent represented by formula (15) or a phenyl group.

[0172] [ka]

[0173] In formula (15), R 19 Each of the -* in formula (15) represents a hydrogen atom or a methyl group. 18 The bond to the phosphorus atom (P) directly connected to the

[0174] When a chloroform solution containing the compound represented by formula (14) at 0.01% by mass is prepared and the absorbance of the chloroform solution is measured using active energy rays including a wavelength of 365 nm (i-line), the absorbance is 0.1 or more, which shows very good absorbency for light with a wavelength of 365 nm (i-line). Therefore, this compound preferably generates radicals for light with a wavelength of 365 nm (i-line). The absorbance is preferably 0.15 or more. The upper limit is, for example, 10.0 or less, and may be 5.0 or less, or 2.0 or less.

[0175] When a chloroform solution containing the compound represented by formula (14) at 0.01% by mass is prepared and the absorbance of the chloroform solution is measured using active energy rays including a wavelength of 405 nm (h-line), the absorbance is 0.1 or more, which shows very good absorbency for light with a wavelength of 405 nm (h-line). Therefore, this compound preferably generates radicals for light with a wavelength of 405 nm (h-line). The absorbance is more preferably 0.15 or more. The upper limit is, for example, 10.0 or less, may be 5.0 or less, or may be 2.0 or less.

[0176] In formula (14), R 18 R each independently represents a substituent represented by formula (15) or a phenyl group. 18 Among these, it is preferable that one or more of them is a substituent represented by formula (15). In formula (15), R 19 R each independently represents a hydrogen atom or a methyl group. 19 Among these, it is preferable that one or more of them is a methyl group, and it is more preferable that all of them are methyl groups.

[0177] Examples of the compound represented by formula (14) include acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred because of its excellent light transmittance. These compounds can be used alone or in combination of two or more.

[0178] Acylphosphine oxides exhibit very good absorbency for active energy rays including those with a wavelength of 405 nm (h-rays), and can suitably radically polymerize the bismaleimide compound (B) and the maleimide compound (C) at a wavelength of 405 nm (h-rays), for example. Therefore, according to this embodiment, it is possible to suitably manufacture a resin composition that does not inhibit a photocuring reaction in an exposure step, has excellent photocurability, and can impart excellent alkaline developability in a development step, and a resin sheet, a multilayer printed wiring board, and a semiconductor device using the same, particularly when used in a multilayer printed wiring board.

[0179] In the resin composition, the content of the photocuring initiator (D) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the resin solids, from the viewpoints of allowing photocuring to proceed sufficiently without inhibiting the photocuring reaction in the resin composition and sufficiently insolubilizing the exposed area in alkaline developability.

[0180] Furthermore, in the case where the resin composition contains the bismaleimide compound (B) and the maleimide compound (C), from the viewpoints of allowing photocuring to proceed sufficiently without inhibiting the photocuring reaction in the resin composition and sufficiently insolubilizing the exposed area in alkali developability, the content of the photocuring initiator (D) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass in total of the bismaleimide compound (B) and the maleimide compound (C).

[0181] [Maleimide compound (E) other than bismaleimide compound (B) and maleimide compound (C)] In the resin composition of this embodiment, a maleimide compound (E) (also referred to as component (E)) other than the bismaleimide compound (B) and the maleimide compound (C) can be used as long as the effects of the present invention are achieved. As described above, the compound (A) and the bismaleimide compound (B) have very good light transmittance, so that even when the maleimide compound (E) is used, light can reach the photocuring initiator sufficiently, and the photoradical reaction of the maleimide can efficiently occur, and photocuring can be performed using various active energy rays. Therefore, even when an active energy ray having a wavelength of 365 nm or an active energy ray having a wavelength of 405 nm is used, the light can reach the photocuring initiator sufficiently, and the radical reaction using the radicals generated from the photocuring initiator can proceed, and photocuring is possible even in a composition containing the maleimide compound (E).

[0182] The maleimide compound (E) is not particularly limited as long as it is a compound other than the bismaleimide compound (B) and the maleimide compound (C) and has one or more maleimide groups in the molecule. For example, N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl- 4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-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-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,Examples of the maleimide compounds (E) include bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethane maleimide, fluorescein-5-maleimide, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These maleimide compounds (E) can be used alone or in a suitable mixture of two or more.

[0183] When the resin composition contains the bismaleimide compound (B) and the maleimide compound (C), the content of the maleimide compound (E) is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C), from the viewpoint of exhibiting excellent photocurability.

[0184] [Filler (F)] In order to improve various properties such as coating properties and heat resistance, the resin composition of this embodiment can contain a filler (F) (also referred to as component (F)). The filler (F) is preferably one that has insulating properties and does not inhibit the permeability to various active energy rays used in photocuring, and more preferably one that does not inhibit the permeability to active energy rays including those with a wavelength of 365 nm (i-rays) and / or 405 nm (h-rays).

[0185] Examples of the filler (F) include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass, E glass, T glass, D glass, etc.), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers (F) can be used alone or in a suitable mixture of two or more kinds.

[0186] Among these, it is preferable to use one or more types selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers (F) may be surface-treated with a silane coupling agent or the like, which will be described later.

[0187] From the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include SFP-130MC (trade name) manufactured by Denka Co., Ltd., and SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by Admatechs Co., Ltd.

[0188] The particle size of the filler (F) is not particularly limited, but from the viewpoint of the ultraviolet light transmittance of the resin composition, it is usually 0.005 to 10 μm, and preferably 0.01 to 1.0 μm.

[0189] In the resin composition, the content of the filler (F) is 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, based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of improving the ultraviolet light transmittance of the resin composition and the heat resistance of the cured product. When the filler is contained, the lower limit is usually 1 part by mass based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of obtaining an effect of improving various properties such as coating properties and heat resistance.

[0190] [Silane coupling agent and wetting / dispersing agent] In the resin composition of the present embodiment, a silane coupling agent and / or a wetting dispersant can be used in combination in order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or resin and the filler. These silane coupling agents are not particularly limited as long as they are generally used for surface treatment of inorganic substances. For example, 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, SSilanes, aminosilanes such as 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; γ-glycidoxypropyl Epoxysilanes such as trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-methylphenyl)silane, vinylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; isocyanate silanes such as tripropyltriethoxysilane; isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl-γ-aminopropyltrimethoxysilane hydrochloride;Examples of the silane coupling agents include acid anhydrides 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 a suitable mixture of two or more.

[0191] The content of the silane coupling agent in the resin composition is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0192] The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paint.Specific examples include DISPERBYK (registered trademark)-110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), 161 (trade name), BYK (registered trademark)-W996 (trade name), W9010 (trade name), and W903 (trade name) manufactured by BYK-Chemie Japan Co., Ltd.These wetting dispersants can be used alone or in a suitable mixture of two or more kinds. In the resin composition, the content of the wetting and dispersing agent is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0193] [Cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds] In this embodiment, as long as the effects of the present invention are achieved, various types of compounds and resins such as cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds other than the compound (A), bismaleimide compound (B), maleimide compound (C), photocuring initiator (D), and maleimide compound (E) can be used depending on the properties of the cured product, such as flame retardancy, heat resistance, and thermal expansion properties. In addition, it is preferable that these compounds and resins are photosensitive to the resin composition and photocured when exposed to active energy rays including a wavelength of 365 nm (i-rays) and / or active energy rays including a wavelength of 405 nm (h-rays). These compounds and resins may be used alone or in appropriate mixture of two or more.

[0194] <Cyanate ester compounds> The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in the molecule substituted with at least one cyanato group (cyanate ester group).

[0195] For example, the one represented by formula (28) can be mentioned.

[0196] [ka]

[0197] In formula (28), Ar1 represents a benzene ring, a naphthalene ring, or two benzene rings bonded together. When there are a plurality of Ar1, they may be the same or different. Each of Ra independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a group in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded together. The aromatic ring in Ra may have a substituent, and the positions of the substituents in Ar1 and Ra may be selected at any positions. p represents the number of cyanato groups bonded to Ar1, and each of p represents an integer of 1 to 3. q represents the number of Ra bonded to Ar1, and is 4-p when Ar1 is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are bonded together. t represents the average number of repetitions, and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t's. When there are multiple X's, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (in which a hydrogen atom may be substituted with a heteroatom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN-, where R represents an organic group), a carbonyl group (-CO-), a carboxy group (-C(=O)O-), a carbonyl dioxide group (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom, or a divalent oxygen atom.

[0198] The alkyl group in Ra in the formula (28) may have either a straight or branched chain structure or a cyclic structure (for example, a cycloalkyl group, etc.). Furthermore, the hydrogen atoms in the alkyl group in formula (28) and the aryl group in Ra may be substituted with halogen atoms such as fluorine atoms and chlorine atoms, alkoxyl groups such as methoxy groups and phenoxy groups, or cyano groups.

[0199] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group. Specific examples of the alkenyl group include a vinyl group, a (meth)allyl group, an isopropenyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butadienyl group, a 2-methyl-2-propenyl group, a 2-pentenyl group, and a 2-hexenyl group. Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

[0200] Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of formula (28) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidodiyl group, etc. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, etc. Examples of the divalent organic group having 1 to 10 nitrogen atoms for X in the formula (28) include an imino group and a polyimide group.

[0201] In addition, examples of the organic group of X in formula (28) include those having a structure represented by formula (29) and those having a structure represented by formula (30).

[0202] [ka]

[0203] In formula (29), Ar2 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and may be the same or different 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 are selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer of 0 to 5.

[0204] [ka]

[0205] In formula (30), Ar3 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and may be the same or different 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 alkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds having different v's.

[0206] Furthermore, examples of X in the formula (28) include divalent groups represented by the following formulas:

[0207] [ka]

[0208] In the formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of Ar2 in formula (29) and Ar3 in formula (30) include a benzenediyl group in which two carbon atoms shown in formula (29) or two oxygen atoms shown in formula (30) are bonded to the 1,4-positions or 1,3-positions, a biphenyldiyl group in which two carbon atoms or two oxygen atoms are bonded to the 4,4'-positions, 2,4'-positions, 2,2'-positions, 2,3'-positions, 3,3'-positions, or 3,4'-positions, and a naphthalenediyl group in which two carbon atoms or two oxygen atoms are bonded to the 2,6-positions, 1,5-positions, 1,6-positions, 1,8-positions, 1,3-positions, 1,4-positions, or 2,7-positions. The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf, and Rg in formula (29), and Ri and Rj in formula (30) have the same meanings as in formula (28).

[0209] Specific examples of the cyanato-substituted aromatic compound represented by formula (28) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4-, or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-(4-cyanatophenyl) ... tophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3- Trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethy 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methoxynaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl)propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2,2-bis(4-cyanatophenyl)hexafluoropropane, 2,2-bis(4-cyanato-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanatophenyl)butane, 1,1-bis(4-cyanatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl)-3-methylbutane, 1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane, 2,2-bis(4-cyanatophenyl)hexane, 2 ,2-bis(4-cyanatophenyl)-3-methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylpentane 4,4-bis(4-cyanatophenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2-methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanatophenyl)phenylmethane, 1,1-bis(4-cyanatophenyl) 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis(4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,4-Bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoic acid-4-cyanatophenyl ester) benzoate), bis-(4-cyanatophenyl)carbonate, 1,3-bis(4-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanatophenyl)fluorene, 9,9-bis(4-cyanato-3-methylphenyl) nyl)fluorene, 9,9-bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane, 1,1,1-tris(4-cyanatophenyl)ethane, 1,1,3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N -Methyl-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,Examples of the phthalimidine include 3-bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1-methyl-3,3-bis(4-cyanatophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanatophenyl)indolin-2-one.

[0210] These cyanate ester compounds can be used alone or in a suitable mixture of two or more.

[0211] Other specific examples of the cyanate ester compound represented by formula (28) include phenol novolak resins and cresol novolak resins (produced by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution by a known method), trisphenol novolak resins (produced by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene novolak resins (produced by reacting a fluorenone compound with 9,9-bis(hydrogen) compound), and the like. aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, and biphenyl aralkyl resins (resulting from a reaction of a bishalogenomethyl compound represented by Ar4-(CH2Y)2 (Ar4 represents a phenyl group, and Y represents a halogen atom; the same applies in the rest of this paragraph) with a phenol compound in the presence of an acid catalyst or without a catalyst by a known method, bis(aryl)fluorenes represented by Ar4-(CH2OR)2 (R represents an alkyl group), Examples of the phenolic resin include a phenolic resin obtained by reacting a bis(hydroxymethyl) compound represented by Ar4-(CH2OH)2 with a phenolic compound in the presence of an acid catalyst, a bis(hydroxymethyl) compound represented by Ar4-(CH2OH)2 with a phenolic compound in the presence of an acid catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound, and a phenolic compound), a phenol-modified xylene formaldehyde resin (a xylene formaldehyde resin obtained by reacting a phenolic compound with a phenolic compound in the presence of an acid catalyst by a known method), a modified naphthalene formaldehyde resin (a naphthalene formaldehyde resin obtained by reacting a hydroxy-substituted aromatic compound with an acid catalyst by a known method), a phenol-modified dicyclopentadiene resin, or a phenolic resin having a polynaphthylene ether structure (a polyhydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is dehydrated and condensed in the presence of a basic catalyst by a known method), which is cyanated by the same method as above, and prepolymers thereof. These cyanate ester compounds can be used alone or in a suitable mixture of two or more.

[0212] The method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. Specific examples include a method in which a hydroxyl group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxyl group is modified by a known method to form a cyanate. Examples of the method for forming a cyanate from a hydroxyl group include the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

[0213] Cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

[0214] In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the cyanate ester compound is 0.01 to 40 parts by mass relative to 100 parts by mass in total of the bismaleimide compound (B) and the maleimide compound (C).

[0215] <Phenol resin> As the phenolic resin, any known phenolic resin can be used as long as it has two or more hydroxyl groups in one molecule. For example, bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac type phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac 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, polymerizable unsaturated hydrocarbon group-containing phenolic resin, and hydroxyl group-containing silicone resin can be mentioned. These phenolic resins can be used alone or in a suitable mixture of two or more.

[0216] In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the phenol resin is 0.01 to 40 parts by mass per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C).

[0217] <Oxetane resin> As the oxetane resin, generally known ones can be used. For example, alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, and 3,3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane, and 3,3-di(trifluoromethyl)perfluoro oxetane, OroExamples of the oxetane resin include oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.), and OXT-221 (trade name, manufactured by Toagosei Co., Ltd.). These oxetane resins can be used alone or in a suitable mixture of two or more kinds.

[0218] In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the oxetane resin is 0.01 to 40 parts by mass per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C).

[0219] <Benzoxazine compounds> As the benzoxazine compound, any generally known compound having two or more dihydrobenzoxazine rings in one molecule can be used. For example, bisphenol A benzoxazine BA-BXZ (Konishi Chemical Industry Co., Ltd., trade name), bisphenol F benzoxazine BF-BXZ (Konishi Chemical Industry Co., Ltd., trade name), bisphenol S benzoxazine BS-BXZ (Konishi Chemical Industry Co., Ltd., trade name), and phenolphthalein benzoxazine can be mentioned. These benzoxazine compounds can be used alone or in a suitable mixture of two or more.

[0220] In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the benzoxazine compound is 0.01 to 40 parts by mass per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C).

[0221] <Epoxy resin> The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, xylene novolac type epoxy resins, multifunctional phenol type epoxy resins, naphthalene type epoxy resins, naphthalene skeleton modified novolac type epoxy resins, naphthylene ether type epoxy resins, phenol aralkyl type epoxy resins, anthracene type epoxy resins, trifunctional phenol type epoxy resins, tetrafunctional phenol type epoxy resins, triglyceride ... Examples of the epoxy resins include diisocyanurate, glycidyl ester type epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, naphthol aralkyl novolac type epoxy resins, aralkyl novolac type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds in which the double bonds of butadiene, etc. are epoxidized, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in a suitable mixture of two or more.

[0222] As the epoxy resin, commercially available products can be used, and examples thereof include an epoxy resin represented by formula (31) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., in which n5 is about 4) and a naphthalene-type epoxy resin represented by formula (32) (HP-4710 (trade name) manufactured by DIC Corporation).

[0223] [ka]

[0224] [ka]

[0225] These epoxy resins can be used alone or in a suitable mixture of two or more kinds.

[0226] In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the epoxy resin is 0.01 to 40 parts by mass per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C).

[0227] <Other compounds> Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; triallyl isocyanurate, trimethallyl isocyanurate, and bisallylnadimide, etc. These compounds can be used alone or in appropriate mixtures of two or more. In the resin composition, when the bismaleimide compound (B) and the maleimide compound (C) are contained, the content of the other compounds is 0.01 to 40 parts by mass per 100 parts by mass of the total of the bismaleimide compound (B) and the maleimide compound (C).

[0228] [Organic Solvent] The resin composition of the present embodiment may contain an organic solvent as necessary. By using an organic solvent, the viscosity during preparation of the resin composition can be adjusted. The type of organic solvent is not particularly limited as long as it can dissolve a part 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, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; aromatic group-containing phenol solvents 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.

[0229] Among these, methyl ethyl ketone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred from the viewpoint of exhibiting excellent solubility for the compound (A) and also for other resins and compounds. These organic solvents may be used alone or in combination of two or more.

[0230] [Other ingredients] In the resin composition of this embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, as well as elastomers, which have not been mentioned so far; flame-retardant compounds, which have not been mentioned so far; additives, etc. can be used in combination, as long as the characteristics of this embodiment are not impaired. These are not particularly limited as long as they are commonly used. For example, flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphorus-based compounds such as phosphate compounds of phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. Examples of additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, gloss agents, polymerization inhibitors, and heat curing accelerators. These components can be used alone or in a suitable mixture of two or more. In the resin composition, the content of each of the other components is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0231] [Method of producing resin composition and varnish] The resin composition of the present embodiment can be prepared by appropriately mixing the compound (A), and, as necessary, the bismaleimide compound (B), the maleimide compound (C), the photocuring initiator (D), the maleimide compound (E), the filler (F), and other resins, other compounds, additives, etc. Examples of methods for producing the resin composition include a method in which the above-mentioned components are sequentially mixed in a solvent and thoroughly stirred.

[0232] When producing the resin composition, known treatments (such as stirring, mixing, and kneading) for uniformly dissolving or dispersing each component can be performed as necessary. Specifically, by performing stirring and dispersion treatment using a stirring tank equipped with a stirrer having appropriate stirring ability, the dispersibility of each component such as compound (A) in the resin composition can be improved. Stirring, mixing, and kneading treatments can be appropriately performed using known devices such as a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll mill, a ball mill, a bead mill, and a sand mill, or a revolving or rotating type mixer. In addition, when preparing the resin composition, an organic solvent can be used as necessary. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples are as described above.

[0233] The resin composition can be suitably used as a varnish for producing the resin sheet of the present embodiment described later. The varnish can be obtained by a known method. For example, the varnish can be obtained by adding 10 to 900 parts by mass, preferably 30 to 500 parts by mass, of an organic solvent to 100 parts by mass of the components in the resin composition excluding the organic solvent, and performing the known treatments (stirring, mixing, kneading, etc.). The organic solvent used for preparing the varnish is not particularly limited, and specific examples thereof are as described above.

[0234] [Application] The resin composition of the present embodiment can be suitably used for the preparation of a multilayer printed wiring board, and can be preferably used in applications requiring an insulating resin composition. For example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins. Among these, the resin composition has excellent photocurability and alkaline developability, and can therefore be suitably used for the insulating layer of a multilayer printed wiring board or for the solder resist.

[0235] [Cured product] The cured product is obtained by curing the resin composition. For example, the resin composition is melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using light. The light wavelength range is preferably in the range of 100 to 500 nm, where curing is efficiently promoted by a photopolymerization initiator or the like.

[0236] [Resin sheet] The resin sheet of the present embodiment is a resin sheet with a support, which has a support and a resin layer disposed on one or both sides of the support, and the resin layer contains the resin composition of the present embodiment. The resin sheet can be produced by applying the resin composition onto the support and drying it. The resin layer in the resin sheet has excellent photocurability and alkali developability.

[0237] The support can be any known one, and is not particularly limited, but is preferably a resin film. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetyl acetate film. Among them, PET film is preferred.

[0238] The resin film is preferably coated with a release agent on its surface to facilitate peeling from the resin layer. 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. If the thickness is less than 5 μm, the support tends to be easily torn when peeling the support before alkaline development, and if the thickness exceeds 100 μm, the resolution when exposing from above the support tends to decrease.

[0239] In order to reduce scattering of light during exposure, the resin film is preferably one having excellent transparency.

[0240] Furthermore, in the resin sheet, the resin layer may be protected with a protective film. By protecting the resin layer side with a protective film, it is possible to prevent adhesion of dirt and the like to the surface of the resin layer and scratches. As the protective film, a film made of the same material as the resin film can be used. 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. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the cost efficiency tends to decrease. In addition, it is preferable that the adhesive strength between the resin layer and the protective film is smaller than the adhesive strength between the resin layer and the support.

[0241] Examples of the method for producing a resin sheet include a method in which a resin composition is applied to a support such as a PET film, and the resin composition is dried to remove the organic solvent, thereby producing a resin sheet. The coating method can be a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater, etc. Drying can be performed, for example, by a method of heating in a dryer at 60 to 200° C. for 1 to 60 minutes.

[0242] The amount of organic solvent remaining in the resin layer is preferably 5% by mass or less based on the total mass of the resin layer from the viewpoint of preventing the organic solvent from diffusing in a later step, and the thickness of the resin layer is preferably 1 to 50 μm from the viewpoint of improving handleability.

[0243] The resin sheet can be preferably used for producing an insulating layer of a multilayer printed wiring board.

[0244] [Multilayer printed wiring board] The multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. The insulating layer can be obtained, for example, by stacking one or more resin sheets and curing them. The number of insulating layers and conductor layers can be appropriately set according to the intended use. The order of the insulating layers and conductor layers is not particularly limited. The conductor layer may be a metal foil used in various printed wiring board materials, for example, a metal foil such as copper and aluminum. Examples of copper metal foil include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is usually 1 to 100 μm. Specifically, it can be produced by the following method.

[0245] (Lamination process) In the lamination process, the resin layer side of the resin sheet is laminated on one or both sides of the circuit board using a vacuum laminator. Examples of the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. The circuit board refers to a board on which a patterned conductor layer (circuit) is formed on one or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit board. The insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by stacking and curing one or more resin sheets of the present embodiment, or may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and one or more known resin sheets different from the resin sheet of the present embodiment. The method of stacking the resin sheet of the present embodiment and the known resin sheet different from the resin sheet of the present embodiment is not particularly limited. The surface of the conductor layer may be roughened in advance by blackening and / or copper etching. In the lamination process, when the resin sheet has a protective film, the protective film is peeled off and then the resin sheet and the circuit board are preheated as necessary, and the resin layer of the resin sheet is pressure-bonded to the circuit board while being pressurized and heated. In this embodiment, a method of laminating the resin layer of the resin sheet to the circuit board under reduced pressure by a vacuum lamination method is preferably used.

[0246] The conditions for the lamination process are, for example, a pressure bonding temperature (lamination temperature) of 50 to 140°C and a pressure bonding pressure of 1 to 15 kgf / cm 2 It is preferable to laminate under reduced pressure with a pressure bonding time of 5 to 300 seconds and an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd.

[0247] (Exposure process) In the exposure step, after the resin layer is provided on the circuit board in the lamination step, a predetermined portion of the resin layer is irradiated with active energy rays from a light source to cure the irradiated portion of the resin layer. Compound (A) does not inhibit the photocuring reaction in the exposure step. The irradiation may be performed through a mask pattern, or a direct writing method may be used in which the radiation is directly irradiated. Examples of the active energy rays include ultraviolet rays, visible light rays, electron beams, and X-rays. The wavelength of the active energy rays is, for example, in the range of 200 to 600 nm. When ultraviolet rays are used, the radiation dose is generally 10 to 1000 mJ / cm. 2 In addition, when a printed wiring board having a high-density and high-definition wiring pattern is manufactured using a stepper exposure method, it is preferable to use, as the active energy ray, an active energy ray having a wavelength of 365 nm (i-ray). When an active energy ray having a wavelength of 365 nm (i-ray) is used, the irradiation amount is about 10 to 10,000 mJ / cm. 2 When a printed wiring board having a high-density and high-definition wiring pattern is manufactured using a direct writing exposure method, it is preferable to use, for example, an active energy ray having a wavelength of 405 nm (h-ray). When an active energy ray having a wavelength of 405 nm (h-ray) is used, the irradiation amount is about 10 to 10,000 mJ / cm 2 It is. The exposure method through a mask pattern includes a contact exposure method in which the mask pattern is closely attached to the multilayer printed wiring board, and a non-contact exposure method in which the mask pattern is not closely attached to the multilayer printed wiring board and the exposure is performed using parallel light, and either method may be used. In addition, when a support exists on the resin layer, the exposure may be performed from above the support, or after the support is peeled off.

[0248] (Alkaline development process) When no support is present on the resin layer, after the exposure step, the non-photocured portion (unexposed portion) is directly removed by alkaline development, and then development is performed to form a pattern of the insulating layer. Furthermore, when a support is present on the resin layer, after the exposure step, the support is removed, and then the non-photocured portion (unexposed portion) is removed by alkaline development, followed by development, whereby a pattern of the insulating layer can be formed. Since the unexposed resin layer containing the resin composition of the present embodiment contains the compound (A), it has excellent alkali developability and the unexposed resin composition can be quickly removed, so that a printed wiring board having a high-definition pattern can be obtained.

[0249] In the case of alkaline development, the developer is not particularly limited as long as it selectively dissolves the unexposed portion, and 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 are used. In this embodiment, it is more preferable to use tetramethylammonium hydroxide aqueous solution. These alkaline developers can be used alone or in a suitable mixture of two or more kinds.

[0250] In addition, the alkali development method can be performed by a known method such as dipping, paddle, spray, swing immersion, brushing, and scraping. In forming a pattern, these development methods may be used in combination as necessary. In addition, as a development method, it is preferable to use a high-pressure spray, since the resolution is further improved. When adopting a spray method, the spray pressure is preferably 0.02 to 0.5 MPa.

[0251] (Post-bake process) In this embodiment, after completion of the alkali development step, a post-baking step is performed to form an insulating layer (cured product). Examples of the post-baking step include an ultraviolet ray irradiation step using a high-pressure mercury lamp and a heating step using a clean oven, and these steps can be used in combination. When irradiating with ultraviolet rays, the amount of irradiation can be adjusted as necessary, for example, 0.05 to 10 J / cm. 2The heating conditions can be appropriately selected according to need, but are preferably selected within the range of 150 to 220° C. for 20 to 180 minutes, and more preferably 160 to 200° C. for 30 to 150 minutes.

[0252] (Conductor layer formation process) After forming an insulating layer (cured product), a conductor layer is formed on the surface of the insulating layer by dry plating. In addition, when forming the conductor layer, the surface of the insulating layer may be subjected to a surface modification treatment before dry plating. As the surface modification treatment, a known method such as a plasma etching treatment, a reverse sputtering treatment, or a corona treatment can be used. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the vapor deposition (vacuum vapor deposition) method, for example, a multilayer printed wiring board is placed in a vacuum chamber, and a metal is heated and evaporated to form a metal film on an insulating layer. In the sputtering method, for example, a multilayer printed wiring board is placed in a vacuum chamber, an inert gas such as argon is introduced, and a direct current voltage is applied to cause the ionized inert gas to collide with a target metal, and a metal film can be formed on an insulating layer by the metal that is knocked out.

[0253] Next, a conductor layer is formed by electroless plating, electrolytic plating, etc. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. can be used.

[0254] [Semiconductor Devices] The semiconductor device of this embodiment includes 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 wiring board. Here, the conductive portion refers to a portion of the multilayer printed wiring board that transmits an electric signal, and the conductive portion may be located on the surface or embedded. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

[0255] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specific examples include a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF) mounting method.

[0256] Also, a semiconductor device can be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which a semiconductor chip is mounted. The substrate on which the semiconductor chip is mounted may be in the form of a wafer or a panel. After formation, the substrate can be manufactured using the same method as that for the multilayer printed wiring board. EXAMPLES

[0257] The present embodiment will be described in more detail below using examples and comparative examples, but the present embodiment is not limited to the following examples.

[0258] [Synthesis of maleimide compound (TMDM)] [Synthesis Example 1] The compound (TMDM) represented by formula (21) was synthesized as follows. [Synthesis of amide acid compound (hereinafter abbreviated as MA-TMDA)] First, MA-TMDA represented by formula (33) was synthesized by the following method.

[0259] [ka]

[0260] In a 100 mL four-neck flask equipped with an argon inlet, a Dean-Stark apparatus, a Dimroth condenser, and a thermometer, 5.2 g (53 mmol) of maleic anhydride, 20 mL of N-methylpyrrolidone (NMP), and 20 mL of toluene were added, and the mixture was stirred at room temperature (25° C.) under an argon stream to completely dissolve the maleic anhydride. 5.0 g (19 mmol) of TMDA (a mixture of 5-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indan and 6-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indan, manufactured by Nippon Junryo Pharmaceutical Co., Ltd.) and 10 mL of NMP were added to the solution, and the mixture was stirred at room temperature (25° C.) for 17 hours. A portion of the reaction solution was taken, water and ethyl acetate were added, and the mixture was shaken. The organic layer was then taken out and dried over magnesium sulfate. The supernatant was distilled at 40° C. to remove the solvent, yielding a yellow oil. 1 H-NMR measurement confirmed that the compound was MA-TMDA represented by formula (33). The MA-TMDA shown in equation (33) 1 The H-NMR assignments are shown below. 1 The H-NMR chart is shown in Figure 1.

[0261] 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)

[0262] [TMDM synthesis] To the reaction solution, 0.67 g (3.5 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 127° C. for 2.5 hours. After cooling to room temperature (25° C.), the reaction solution after cooling was poured into a mixed solution of 50 mL of saturated aqueous sodium bicarbonate solution and 100 mL of ethyl acetate while stirring. Furthermore, 100 mL of water and 100 mL of ethyl acetate were added, stirred, and allowed to stand for 5 minutes. Then, the liquids were separated, and the aqueous layer was extracted three times with 50 mL of ethyl acetate. All the organic layers were combined and washed once with 100 mL of water, once with 10 mL of saturated saline, and twice with 5 mL of saturated saline. The mixture was dried over magnesium sulfate, and the solid matter was filtered off, and the solvent was distilled off at 40° C. to obtain a yellow solid. The obtained yellow solid was dissolved in 6.5 mL of acetone, and the acetone solution was poured into 300 mL of water. The precipitated solid was collected by filtration, washed with a small amount of isopropyl alcohol (IPA), and then dried under reduced pressure at 50° C. for 20 hours to obtain 5.71 parts by mass of a yellow solid. 1 H-NMR measurement confirmed that the compound was a maleimide compound (TMDM) represented by formula (21). TMDM's 1 The H-NMR assignments are shown below. 1 The H-NMR chart is shown in Figure 2.

[0263] 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)

[0264] [Synthesis of compound represented by formula (16)] [Example 1] A compound represented by formula (16) (also referred to as compound (A-1)) was synthesized as follows. A 200 mL flask was charged with 6.56 g (55.5 mmol) of 1,10-decanediol (Tokyo Chemical Industry Co., Ltd.), 23.10 g (116.6 mmol) of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Company, Inc., H-TMAn (trade name)), 6.77 g (55.5 mmol) of 4-dimethylaminopyridine, 12.35 g of triethylamine, and 60 g of dichloromethane, and the mixture was stirred at room temperature (25° C.) for 7 hours. 100mL of water and 50mL of dichloromethane were added to the reaction solution, and the mixture was stirred for another hour. 150mL of dichloromethane and 50mL of 1M hydrochloric acid were then added, and the mixture was separated, and the aqueous layer was removed. 60mL of 1M hydrochloric acid was added to the resulting organic layer, and the mixture was stirred. After the aqueous layer was removed by separation, the mixture was washed twice with 60mL of 1M hydrochloric acid, once with 60mL of water, and once with 30mL of saturated saline, and then dried over magnesium sulfate to distill off the solvent. The mixture was dried in a vacuum at 80°C, and 10.96g of a white solid was obtained. 1 H-NMR measurement confirmed that the compound was compound (A-1) represented by formula (16). Compound (A-1) 1 The H-NMR assignments are shown below. 1 The H-NMR chart is shown in Figure 3.

[0265] 1 H-NMR (500MHz, DMSO-d6) δ (ppm): 12.30 (s, 4H, -COOH), 3.97 (m, 4H), 3.05 (s, 2H), 2.57 (m, 2H), 2.3-1.1 (m, 32H)

[0266] [Synthesis of compound represented by formula (17)] [Example 2] A compound represented by formula (17) (also referred to as compound (A-2)) was synthesized as follows. A 200 mL flask was charged with 8.71 g (50 mmol) of 1,10-decanediol (Tokyo Chemical Industry Co., Ltd.), 20.81 g (105 mmol) of cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Company, Inc., H-TMAn-S (trade name)), 6.10 g (50 mmol) of 4-dimethylaminopyridine, 11.13 g of triethylamine, and 60 g of dichloromethane, and the mixture was stirred at room temperature (25° C.) for 3 hours. 50 mL of water and 6 mL of methanol were added to the reaction solution and stirred for another hour. 100 mL of 1M hydrochloric acid was added and stirred, and the aqueous layer was removed, and then 100 mL of 1M hydrochloric acid was added and stirred. The aqueous layer was removed again, and 100 mL of 1M hydrochloric acid was added. The precipitated white solid was collected by suction filtration and washed three times with 200 mL of water. 18.84 g of white solid was obtained by vacuum drying at 40°C. 1 H-NMR measurement confirmed that the compound was compound (A-2) represented by formula (17). Compound (A-2) 1 The H-NMR assignments are shown below. 1 The H-NMR chart is shown in Figure 4.

[0267] 1 H-NMR (500MHz, DMSO-d6) δ (ppm): 12.23 (s, 4H, -COOH), 3.97 (m, 4H), 3.05 (m, 2H), 2.57 (m, 2H), 2.3-1.1 (m, 32H)

[0268] [Synthesis of compound represented by formula (18)] [Example 3] A compound represented by formula (18) (also referred to as compound (A-3)) was synthesized as follows. A 200 mL flask was charged with 5.91 g (50 mmol) of 1,6-hexanediol (Tokyo Chemical Industry Co., Ltd.), 20.81 g (105 mmol) of cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Company, Inc., H-TMAn-S (trade name)), 6.10 g (50 mmol) of 4-dimethylaminopyridine, 11.13 g of triethylamine, and 60 g of dichloromethane, and the mixture was stirred at room temperature (25° C.) for 8 hours. 50 mL of water was added to the reaction solution, and the mixture was stirred for another hour, after which 50 mL of 1M hydrochloric acid was added. 100 mL of methyl isobutyl ketone and 100 mL of 1M hydrochloric acid were added, and the aqueous layer was removed. 200 mL of 1M hydrochloric acid was added to the obtained organic layer, and the precipitated white solid was collected by suction filtration. The collected solid was washed twice with 70 mL of 1M hydrochloric acid and twice with 100 mL of water, and vacuum dried at 50°C to obtain 18.40 g of a white solid. 1 H-NMR measurement confirmed that the compound was compound (A-3) represented by formula (18). Compound (A-3) 1 The H-NMR assignments are shown below. 1 The H-NMR chart is shown in Figure 5.

[0269] 1 H-NMR (500MHz, DMSO-d6) δ (ppm): 12.24 (s, 4H, -COOH), 3.98 (m, 4H), 3.05 (m, 2H), 2.57 (m, 2H), 2.3-1.1 (m, 22H)

[0270] [Raw material evaluation] [Transmittance and absorbance] Compound (A-1) was used as compound (A), and an N-methylpyrrolidone solution containing 1 mass% of compound (A-1) was prepared. The transmittance at wavelengths of 365 nm and 405 nm was measured using a UV-vis measurement device (Hitachi Spectrophotometer U-4100, manufactured by Hitachi High-Technologies Corporation). Similarly, using compound (A-2) or compound (A-3) as compound (A), the absorbance at wavelengths of 365 nm and 405 nm was measured.

[0271] As the bismaleimide compound (B), MIZ-001 (trade name, mass average molecular weight (Mw): 3000) manufactured by Nippon Kayaku Co., Ltd. was used. A chloroform solution containing 1 mass% of this MIZ-001 (trade name) was prepared, and the transmittance at wavelengths of 365 nm and 405 nm was measured using a UV-vis measurement device (Hitachi Spectrophotometer U-4100 (trade name) manufactured by Hitachi High-Technologies Corporation).

[0272] Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad (registered trademark) 819 (product name) manufactured by IGM Resins BV) was used as the photocuring initiator (D), and a chloroform solution containing 0.01 mass% of this Omnirad (registered trademark) 819 (product name) was prepared. The absorbance at wavelengths of 365 nm and 405 nm was measured using a UV-vis measurement device (U-4100 (product name)). The results are shown in Table 1.

[0273] [Table 1]

[0274] [Example 4] (Preparation of resin composition and resin sheet) As the compound (A), 10 parts by mass of compound (A-1), as the bismaleimide compound (B), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000) manufactured by Nippon Kayaku Co., Ltd., as the maleimide compound (C), 25 parts by mass of BCPH13 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd. as the maleimide compound (C), 15 parts by mass of TMDM as the maleimide compound (C), and 5 parts by mass of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV) as the photocuring initiator (D) were mixed, and 172.5 parts by mass of methyl ethyl ketone (manufactured by Idemitsu Kosan Co., Ltd.) was added, and the mixture was heated and stirred using a 70 ° C. water bath to obtain a varnish (resin composition). This varnish was dropped onto a 38 μm thick PET film (Unipeel (registered trademark) TR1-38 (product name) manufactured by Unitika Ltd.) and a coating film was formed by spin coating (300 rpm for 10 seconds, then 1000 rpm for 30 seconds). The resulting coating film was dried at 90° C. for 5 minutes to obtain a resin sheet having a PET film as a support and a resin layer of 10 μm in thickness.

[0275] (Preparation of resin for evaluation) The resin surfaces of the obtained resin sheets were laminated together, and a vacuum was applied for 30 seconds (5.0 hPa or less) using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.), and then a pressure of 10 kgf / cm was applied. 2 The laminate was then molded at 70°C for 30 seconds under a pressure of 7kgf / cm. 2 Then, lamination molding was performed at a temperature of 70° C. for 60 seconds to obtain a resin for evaluation having supports on both sides.

[0276] (Creating inner layer circuit boards) A glass cloth-based BT (bismaleimide-triazine) resin double-sided copper-clad laminate (copper foil thickness 18 μm, thickness 0.2 mm, CCL (registered trademark)-HL832NS (product name) manufactured by Mitsubishi Gas Chemical Co., Inc.) with an inner layer circuit formed thereon was subjected to a copper surface roughening treatment on both sides using CZ8100 (product name) manufactured by MEC Co., Ltd. to obtain an inner layer circuit board.

[0277] (Preparation of Laminate for Evaluation) The resin surface of the obtained resin sheet was placed on the copper surface (one side) of the inner layer circuit board, and a vacuum was applied (5.0 hPa or less) for 30 seconds using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.), and then a pressure of 10 kgf / cm was applied. 2 The laminate was then molded at 70°C for 30 seconds under a pressure of 10kgf / cm. 2 Then, lamination molding was performed at a temperature of 70° C. for 60 seconds to obtain a laminate for evaluation in which an inner layer circuit board, a resin layer, and a support were laminated.

[0278] [Example 5] Except for using 7.5 parts by mass of compound (A-1) instead of 10 parts by mass of compound (A-1) and 168.8 parts by mass of methyl ethyl ketone instead of 172.5 parts by mass of methyl ethyl ketone, a varnish and a resin sheet were obtained in the same manner as in Example 4. In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0279] [Example 6] Except for using 7.5 parts by mass of compound (A-2) instead of 10 parts by mass of compound (A-1) as compound (A), and using 168.8 parts by mass of methyl ethyl ketone instead of 172.5 parts by mass of methyl ethyl ketone, a varnish and a resin sheet were obtained in the same manner as in Example 4. In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0280] [Example 7] Except for using 5 parts by mass of compound (A-2) instead of 10 parts by mass of compound (A-1) as compound (A), and using 165.0 parts by mass of methyl ethyl ketone instead of 172.5 parts by mass of methyl ethyl ketone, a varnish and a resin sheet were obtained in the same manner as in Example 4. In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0281] [Example 8] Except for using 7.5 parts by mass of compound (A-3) instead of 10 parts by mass of compound (A-1) as compound (A), and using 168.8 parts by mass of methyl ethyl ketone instead of 172.5 parts by mass of methyl ethyl ketone, a varnish and a resin sheet were obtained in the same manner as in Example 4. In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0282] [Example 9] Except for using 5 parts by mass of compound (A-3) instead of 10 parts by mass of compound (A-1) as compound (A), and using 165.0 parts by mass of methyl ethyl ketone instead of 172.5 parts by mass of methyl ethyl ketone, a varnish and a resin sheet were obtained in the same manner as in Example 4. In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0283] [Comparative Example 1] A varnish and a resin sheet were obtained in the same manner as in Example 4, except that 10 parts by mass of 1,10-decanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 10 parts by mass of compound (A-1). In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0284] [Comparative Example 2] A varnish and a resin sheet were obtained in the same manner as in Example 4, except that 10 parts by mass of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 10 parts by mass of compound (A-1). In addition, a resin for evaluation and a laminate for evaluation were obtained in the same manner as in Example 4 using the resin sheet.

[0285] 〔evaluation〕 The evaluation resins and evaluation laminates obtained in the examples and comparative examples were measured and evaluated by the following methods. The results are shown in Table 2 and FIG. <Light curing> Using a photo DSC (DSC-2500 (trade name) manufactured by TA Instruments Japan, Inc.) equipped with a light source (Omnicure (registered trademark) S2000 (trade name) manufactured by U-VIX Corporation) capable of irradiating active energy rays with wavelengths ranging from 200 to 600 nm, the obtained evaluation resin was irradiated with active energy rays with wavelengths ranging from 200 to 600 nm at an illuminance of 30 mW for an exposure time of 3.5 minutes, and a graph was obtained with the horizontal axis representing time (sec) and the vertical axis representing heat flow (mW). In addition, a graph was obtained with the horizontal axis representing time (sec) and the vertical axis representing heat flow (mW) under the same conditions as above, except that a 405 nm wavelength (h-line) filter was used as the light source and active energy rays containing a 405 nm wavelength (h-line) were used. In each graph, the peak area when a horizontal line was drawn from the end point of the graph was taken as the enthalpy (J / g). The curability was evaluated according to the following criteria. "AA": Enthalpy was 1 (J / g) or more. "CC": The enthalpy was less than 1 (J / g). Incidentally, an enthalpy of 1 (J / g) or more means that curing of the resin proceeds sufficiently by exposure to light of a predetermined wavelength.

[0286] <Alkaline developability> The obtained laminate for evaluation was irradiated with active energy rays including a wavelength of 405 nm (h-rays) from above the support using a light source (MA-20 (product name) manufactured by Mikasa Co., Ltd.) at an irradiation dose of 300 mJ / cm. 2 The resin layer was exposed to light at 1000 nm, and the remaining portion was left unexposed. The support (PET film) was then peeled off, and the resin layer was shaken in a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) (developer, manufactured by Tokuyama Corporation) for 180 seconds. The alkaline developability was evaluated visually according to the following criteria. "AA": The exposed area was insoluble, but the unexposed area dissolved after shaking for 180 seconds. "AB": The exposed area was insoluble. The unexposed area was partially dissolved after 180 seconds of shaking, but some remained undissolved. "CC": Both exposed and unexposed areas were insoluble. Photographs of the resin sheets obtained in Example 4 and Comparative Example 1 after alkali development are shown in FIG.

[0287] [Table 2]

[0288] As is clear from Table 2, according to this embodiment, the composition is well sensitized and photocured when exposed to either an active energy ray having a wavelength of 405 nm (h-ray) or an active energy ray having a wavelength of 200 to 600 nm. Furthermore, according to this embodiment, a cured product having excellent alkali developability can be obtained.

[0289] This application is based on a Japanese patent application (Patent Application No. 2019-223952) filed on December 11, 2019, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0290] The resin composition of the present embodiment can be suitably used for the production of a multilayer printed wiring board, and can be preferably used for applications requiring an insulating resin composition, and is therefore industrially useful. Specifically, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

Claims

1. A compound (A) represented by the following formula (1): 【Chemistry 1】 (In formula (1), R 1 each independently represents a group represented by the following formula (2) or a hydrogen atom; R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 1 At least one of the above is a group represented by the following formula (2): 【Chemistry 2】 (In formula (2), -* represents a bond.)

2. The R 1 The compound (A) according to claim 1, wherein at least one of the above is a group represented by the following formula (3): 【Chemistry 3】 (In formula (3), -* represents a bond.)

3. An alcohol compound represented by the following formula (4), A method for producing the compound (A) according to claim 1 or 2, comprising a step of reacting with an acid anhydride represented by the following formula (5): 【Chemistry 4】 (In formula (4), R 3 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 【Chemistry 5】

4. The method according to claim 3 , wherein the acid anhydride represented by formula (5) includes an acid anhydride represented by the following formula (6): 【Chemistry 6】

5. A resin composition comprising the compound (A) according to claim 1 or 2.

6. The resin composition according to claim 5, further comprising a bismaleimide compound (B) containing a structural unit represented by the following formula (7) and maleimide groups at both ends of the molecular chain: 【Chemistry 7】 (In formula (7), R 4 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 5 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 6 Each of n independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. 1 each independently represents an integer of 1 to 10.

7. The resin composition according to claim 5 or 6, further comprising at least one maleimide compound (C) selected from the group consisting of a compound represented by the following formula (8), a compound represented by the following formula (9), a compound represented by the following formula (10), a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13). 【Chemistry 8】 (In formula (8), R 7 , R 8 , and R 9 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent. 【Chemistry 9】 (In formula (9), R 10 , R 11 , and R 12 Each of n independently represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. 2 represents an integer from 1 to 10. 【Chemistry 10】 (In formula (10), R 13 each independently represents a hydrogen atom, a methyl group, or an ethyl group; R 14 each independently represents a hydrogen atom or a methyl group. 【Chemistry 11】 (In formula (11), 15 Each independently represents a hydrogen atom or a methyl group. 3 represents an integer from 1 to 10. 【Chemistry 12】 (In formula (12), R 16 each independently represents a hydrogen atom, a methyl group, or an ethyl group. 【Chemistry 13】 (In formula (13), R 17 Each independently represents a hydrogen atom or a methyl group. 4 represents an integer from 1 to 10.

8. The resin composition according to any one of claims 5 to 7, further comprising a photocuring initiator (D).

9. The resin composition according to claim 8, wherein the photocuring initiator (D) comprises a compound represented by the following formula (14): 【Chemistry 14】 (In formula (14), R 18 each independently represents a group represented by the following formula (15) or a phenyl group. 【Chemistry 15】 (In formula (15), -* represents a bond, and R 19 each independently represents a hydrogen atom or a methyl group.

10. A support; A resin layer disposed on one or both sides of the support, The resin layer comprises the resin composition according to any one of claims 5 to 9. Resin sheet.

11. The resin sheet according to claim 10, wherein the resin layer has a thickness of 1 to 50 μm.

12. An insulating layer; A conductor layer formed on one or both sides of the insulating layer; having A multilayer printed wiring board, wherein the conductor layer comprises the resin composition according to any one of claims 5 to 9.

13. A semiconductor device comprising the resin composition according to any one of claims 5 to 9.

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