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

Abstract

The present invention provides: a resin composition, a resin sheet, a multilayer printed circuit board, and a semiconductor device that do not hinder the photocuring reaction in the exposure process when used for the production of a multilayer printed circuit board, have excellent photocurability to various active energy rays, can impart excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to an adhesive metal such as titanium. The resin composition of the present invention comprises a bismaleimide compound (A) and an imidazole compound (B) represented by the following formula (2), wherein the bismaleimide compound (A) comprises a structural unit represented by the following formula (1) and maleimide groups located at both ends of the molecular chain.

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin sheet, a multilayer printed circuit board and a semiconductor device. Background Art

[0002] Due to the miniaturization and high density of multilayer printed circuit boards, research on thinning the laminate used in multilayer printed circuit boards is becoming popular. As the thickness becomes thinner, the insulating layer is also required to be thinner, and resin sheets without glass cloth are being sought. Among the resin compositions used as materials for the insulating layer, thermosetting resins are the mainstream, and drilling for achieving conduction between the insulating layers is usually performed by laser processing.

[0003] On the other hand, laser-based drilling has the problem that the more holes a high-density substrate has, the longer the processing time is. Therefore, in recent years, the following resin sheet is required: it uses a resin composition that can be cured by irradiation with light (exposure process) and the unexposed part can be removed (development process), so that drilling can be performed at one time through the exposure and development processes.

[0004] As a method of exposure, a method of using a mercury lamp as a light source and exposing through a photomask is used, and a material that can be properly exposed under the light source of the mercury lamp is required. The exposure method using the mercury lamp as a light source uses ghi mixed rays (the wavelength of g rays is 436nm, the wavelength of h rays is 405nm, and the wavelength of i rays is 365nm), etc., and a general photocuring initiator can be selected. In addition, in recent years, as an exposure method, the introduction of a direct drawing exposure method that directly draws a photosensitive resin composition layer without a photomask based on the digital data of the pattern is also underway. The direct drawing exposure method has good accuracy compared to the exposure method through a photomask, and a high-precision pattern can be obtained, so it is particularly suitable for substrates that require high-density wiring formation. Its light source uses monochromatic light such as laser, and in a device of the DMD (digital micromirror device) method that can form a high-precision anti-etching pattern, a light source with a wavelength of 405nm (h rays) is used. Furthermore, in order to obtain a higher-definition pattern, an exposure method using i-rays (wavelength 365 nm) as a light source, which have less chromatic aberration than ghi mixed rays, is also being introduced.

[0005] As a development method, alkali development is used from the viewpoint of obtaining a high-definition pattern.

[0006] In addition, as conductor wiring becomes finer and denser, a method of directly forming a copper thin film on one or both sides of an insulating layer by sputtering, ion plating, vapor deposition, and chemical plating is being used for the conductor layer. However, these methods have the problem that the adhesion between the conductor layer and the insulating layer is significantly reduced when exposed to high temperatures in a reflow process, etc., in a hygroscopic state.

[0007] Therefore, in order to improve the adhesion between the conductor layer and the insulating layer, a method of roughening the surface of the insulating layer by chemicals or physical means is known, but it is difficult to form fine conductor wiring on the roughened insulating layer surface. Therefore, a method of inserting an adhesive metal such as titanium between the conductor layer (copper thin film) and the insulating layer when forming fine conductor wiring is known.

[0008] As a photosensitive resin composition for forming an insulating layer, Patent Document 1 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent).

[0009] In addition, patent document 2 has the record about the resin composition containing the curable resins such as polyvalent carboxyl compound and epoxy resin, and the polyvalent carboxyl compound is obtained by reacting bismaleimide with monoamine and anhydride. And, patent document 2 has the record about the polyvalent carboxyl compound containing that can obtain the cured product with alkali developability.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: WO2018 / 56466A1

[0013] Patent Document 2: Japanese Patent Application Publication No. 2015-229734 Summary of the invention

[0014] Problem that the invention aims to solve

[0015] However, in Patent Document 1, bismaleimide compounds are used as curable resins, but maleimide compounds generally have poor light transmittance, so if maleimide compounds are included, light will not fully reach the photocuring initiator, and the photocuring initiator is difficult to generate free radicals, and its reactivity is very low. Therefore, in Patent Document 1, the maleimide compound is cured by additional heating before development, but due to the accompanying heating, a high-precision pattern cannot be obtained. In addition, there is the following problem: even if an adhesive metal such as titanium is inserted between the conductor layer and the insulating layer, the cured insulating layer cannot obtain sufficient adhesion to the adhesive metal such as titanium, and if it is exposed to high temperature in a hygroscopic state or in a reflow soldering process, the adhesion strength will be significantly reduced. Moreover, the resin composition recorded in Patent Document 1 is not sufficiently alkali developable, so unexposed resin compositions will remain after development. Therefore, a high-precision pattern cannot be obtained in Patent Document 1, and it cannot be used for the manufacture of high-density printed circuit boards.

[0016] Patent document 2 does not have a specific record of the adhesion to adhesive metals such as titanium. Moreover, the polyvalent carboxyl compound must be obtained by reacting bismaleimide with a monoamine and then reacting with an acid anhydride, so the process is complicated. In addition, an aromatic amine compound is used as the monoamine, so the polyvalent carboxyl compound contains an amide group with an aromatic ring in its structure. Therefore, the polyvalent carboxyl compound has poor light transmittance and hinders the photocuring reaction, so it is actually difficult to be used in a photosensitive resin composition.

[0017] Therefore, the present invention has been made in view of the problems of the prior art, and provides a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device which, when used for the production of a multilayer printed wiring board, does not inhibit the photocuring reaction in the exposure process, has excellent photocurability to various active energy rays, can impart excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to an adhesive metal such as titanium.

[0018] Solutions for solving problems

[0019] The present inventors have conducted intensive studies and have found that a resin composition and a resin sheet comprising a specific bismaleimide compound (A) and a specific imidazole compound (B) do not inhibit the photocuring reaction in the exposure process of producing a multilayer printed circuit board, have excellent photocurability to various active energy rays, can be imparted with excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to adhesive metals such as titanium. Therefore, by using them, a high-density printed circuit board with a high-precision pattern and a semiconductor device can be obtained, thereby completing the present invention.

[0020] That is, the present invention includes the following contents.

[0021] [1] A resin composition comprising a bismaleimide compound (A) and an imidazole compound (B) represented by the following formula (2), wherein the bismaleimide compound (A) comprises a structural unit represented by the following formula (1) and maleimide groups located at both ends of the molecular chain.

[0022]

[0023] (In formula (1), R1 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 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. R3 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. n1 each independently represents an integer of 1 to 10.)

[0024]

[0025] (In formula (2), R4 to R7 each independently represent a hydrogen atom, an aldehyde group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and the total number of carbon atoms of R4 to R7 is 8 or more.)

[0026] [2] The resin composition according to [1], wherein the imidazole compound (B) comprises a member selected from the group consisting of 2-undecyl imidazole, 2-heptadecylimidazole, 1-(triphenylmethyl)imidazole, 1-(2,6-diisopropylphenyl)imidazole, 1-(10-hydroxydecyl)imidazole, 1-(2-phenylethyl)-1H-imidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-benzyl-2-methylimidazole, 2,4-diphenyl-1H-imidazole, 4,5-diphenylimidazole, At least one selected from the group consisting of oxadiazole, 1-trityl imidazole-4-carboxaldehyde, 2,4,5-triphenyl imidazole, 2-(4-hydroxyphenyl)-4,5-diphenyl imidazole, 2-(4-fluorophenyl)-4,5-diphenyl imidazole, 2-(2-chlorophenyl)-4,5-diphenyl imidazole, 2-(4-chlorophenyl)-4,5-diphenyl imidazole, 4,5-bis(hydroxymethyl)-2-phenyl imidazole, and 4-(4,5-diphenyl-1H-imidazol-2-yl)benzonitrile.

[0027] [3] The resin composition according to [1] or [2], further comprising a compound (C) having one or more carboxyl groups.

[0028] [4] The resin composition according to [3], wherein the compound (C) containing one or more carboxyl groups includes a compound represented by the following formula (3).

[0029]

[0030] (In formula (3), R8 each independently represents a group represented by the following formula (4) or a hydrogen atom. R9 each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. At least one R8 is a group represented by the following formula (4).)

[0031]

[0032] (In formula (4), -* represents an atomic bond.)

[0033] [5] The resin composition according to any one of [1] to [4], further comprising at least one maleimide compound (D) selected from the group consisting of a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), a compound represented by the following formula (8), a compound represented by the following formula (9), and a compound represented by the following formula (10).

[0034]

[0035] (In formula (5), R 10 , R 11 , and R 12 Each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0036]

[0037] (In formula (6), R 13 , R 14 , and R 15 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.

[0038]

[0039] (In formula (7), R 16 Each independently represents a hydrogen atom, a methyl group, or an ethyl group. 17 Each independently represents a hydrogen atom or a methyl group. )

[0040]

[0041] (In formula (8), R 18 Each independently represents a hydrogen atom or a methyl group. n3 represents an integer of 1 to 10.

[0042]

[0043] (In formula (9), R 19 Each independently represents a hydrogen atom, a methyl group, or an ethyl group. )

[0044]

[0045] (In formula (10), R 20 Each independently represents a hydrogen atom or a methyl group. n4 represents an integer of 1 to 10. )

[0046] [6] The resin composition according to any one of [1] to [5], further comprising a photocuring initiator (E).

[0047] [7] A resin sheet comprising: a support, and a resin layer disposed on one or both surfaces of the support, wherein the resin layer comprises the resin composition according to any one of [1] to [6].

[0048] [8] The resin sheet according to [7], wherein the resin layer has a thickness of 1 to 50 μm.

[0049] [9] A multilayer printed wiring board comprising: an insulating layer and a conductor layer formed on one or both surfaces of the insulating layer, wherein the insulating layer comprises the resin composition according to any one of [1] to [6].

[0050]

[10] A semiconductor device comprising the resin composition according to any one of [1] to [6].

[0051] Effects of the Invention

[0052] The resin composition and resin sheet of the present invention do not inhibit the photocuring reaction in the exposure process of producing a multilayer printed circuit board, have excellent photocurability to various active energy rays, can be imparted with excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to adhesive metals such as titanium. Therefore, by using them, a high-density printed circuit board and a semiconductor device with a high-definition pattern can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 is the photocuring initiator (E1) obtained in Synthesis Example 1 1 H-NMR graph.

[0054] Figure 2 For the amido acid compound (MA-TMDA) 1 H-NMR graph.

[0055] Figure 3 For maleimide compounds (TMDM) 1 H-NMR graph.

[0056] Figure 4 is the compound (C1) obtained in Synthesis Example 3 1 H-NMR graph. DETAILED DESCRIPTION

[0057] Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail. The following this embodiment is an example for illustrating the present invention and is not intended to limit the present invention to the following contents. The present invention can be implemented by appropriately modifying it within the scope of its gist.

[0058] It should be noted that "(meth)acrylic acid" in this specification refers to both "acrylic acid" and its corresponding "methacrylic acid". In addition, in this specification, "resin solid content" or "resin solid content in a resin composition" refers to the components other than the imidazole compound (B), the compound (C) containing one or more carboxyl groups, the photocuring initiator (E), the additive, the solvent, and the filler in the resin composition unless otherwise specified, and "100 parts by mass of resin solid content" means that the total of the components other than the imidazole compound (B), the compound (C) containing one or more carboxyl groups, the photocuring initiator (E), the additive, the solvent, and the filler in the resin composition is 100 parts by mass.

[0059] In this specification, Mw represents a mass average molecular weight, Mn represents a number average molecular weight, and Mw / Mn represents a molecular weight distribution. Mw, Mn, and Mw / Mn can be determined by gel permeation chromatography (GPC) and conversion by polystyrene standards.

[0060] [Resin composition]

[0061] The resin composition of the present embodiment includes a bismaleimide compound (A) (also referred to as component (A) or bismaleimide compound (A)) and an imidazole compound (B) shown in formula (2) (also referred to as component (B) or compound (B)), wherein the bismaleimide compound (A) includes a structural unit shown in formula (1) and a maleimide group at both ends of the molecular chain. The resin composition of the present embodiment includes compound (A) and compound (B), and is suitable for use in the production of multilayer printed circuit boards. By using a resin composition, the photocuring reaction is not hindered in the exposure process of the production of a multilayer printed circuit board, and excellent photocurability is provided to various active energy rays, and excellent alkali developability can be given in the developing process, and the obtained insulating layer has excellent adhesion to metals with adhesive properties such as titanium. As metals with adhesive properties such as titanium, for example, titanium, zirconium oxide, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten, and alloys of these metals can be cited.

[0062] [Bismaleimide compound (A)]

[0063] The resin composition of the present embodiment contains a bismaleimide compound (A) containing a structural unit represented by formula (1) and maleimide groups located at both ends of the molecular chain.

[0064]

[0065] In formula (1), R1 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 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. R3 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. n1 each independently represents an integer of 1 to 10.

[0066] The present inventors presume that the reason why the resin composition has excellent photocurability to various active energy rays (light rays) is as follows, due to the simultaneous inclusion of the imidazole compound (B) and the bismaleimide compound (A) described below.

[0067] Generally, maleimide compounds have poor light transmittance, so if the resin composition contains maleimide compounds, light will not fully reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator will have difficulty in generating free radicals. Therefore, generally, the photoradical reaction of maleimide compounds is difficult to proceed, and even if free radical polymerization and dimerization reactions of maleimide monomers are performed, their reactivity is very low.

[0068] However, the bismaleimide compound (A) has a structural unit shown in formula (1), i.e., an alicyclic skeleton, and therefore has excellent light transmittance. In addition, the imidazole compound (B) does not hinder light transmittance, and in addition, does not participate in the photoradical reaction, and does not react with the bismaleimide compound (A). Therefore, light fully reaches the photocuring initiator, effectively causing the photoradical reaction of maleimide, using various active energy rays, it is possible to photocuring with a compound (C) (also referred to as component (C) or compound (C)) containing more than one carboxyl group, which is mixed as needed, described later, a maleimide compound (D) (also referred to as component (D) or compound (D)), and a photocuring initiator (E) (also referred to as component (E) or initiator (E)) described later.

[0069] For the bismaleimide compound, a chloroform solution containing it by 1% by mass is prepared, and when the transmittance of the chloroform solution containing the bismaleimide compound by 1% by mass is measured using an active energy ray containing a wavelength of 365nm (i-ray), when its transmittance is 5% or more, it shows very excellent light transmittance. In addition, when the transmittance of the chloroform solution containing the bismaleimide compound by 1% by mass is measured using an active energy ray containing a wavelength of 405nm (h-ray), when its transmittance is 5% or more, it shows very excellent light transmittance. Therefore, for example, when a printed circuit board with high density and high-precision wiring formation (pattern) is manufactured using a direct drawing exposure method, even when an active energy ray containing a wavelength of 405nm (h-ray) is used, a photo-radical reaction of maleimide is effectively caused. For the transmittance of a wavelength of 365nm (i-ray), from the perspective of showing better light transmittance, it is preferably 8% or more, and more preferably 10% or more. The transmittance at a wavelength of 405 nm (h-ray) is preferably 8% or more, and more preferably 10% or more, from the perspective of manufacturing a printed circuit board with a higher density and high-precision wiring formation (pattern). It should be noted that the upper limit of the transmittance at a wavelength of 365 nm (i-ray) and the transmittance at a wavelength of 405 nm (h-ray) is, for example, 99.9% or less.

[0070] Generally, the absorbance of the photocuring initiator for the light in the long wavelength region tends to be lower. For example, when using active energy rays (light) containing a wavelength of 405nm (h-rays), the light of this wavelength is a relatively long wavelength, so it will not be absorbed by the usual photocuring initiator. If a photocuring initiator that can properly absorb this light to generate free radicals is not used, polymerization will not proceed. Therefore, as the photocuring initiator (E) described later, it is preferred to use a photocuring initiator that has an absorbance of 0.1 or more for light with a wavelength of 405nm (h-rays) when the absorbance of a chloroform solution containing the photocuring initiator (E) at 0.01% by mass is measured, and exhibits very excellent light absorption.

[0071] As mentioned above, the bismaleimide compound (A) and the imidazole compound (B) have excellent light transmittance, so even when, for example, active energy rays having a wavelength of 365 nm or active energy rays having a wavelength of 405 nm are used, the light will sufficiently reach the photocuring initiator, and a free radical reaction using free radicals generated by the photocuring initiator will proceed, thereby achieving photocuring of a composition containing a large amount of the bismaleimide compound (A).

[0072] Generally, maleimide compounds have very low water solubility and are not reactive with the alkali component in the alkali developer, so it is difficult to obtain alkali developability. However, by making the resin composition contain bismaleimide compound (A) and imidazole compound (B), it has excellent photocurability and very good alkali developability. The reason is still uncertain, but the present inventors speculate as follows.

[0073] That is, the bismaleimide compound (A) has a relatively long chain and soft structure, and does not have a structure that causes interaction with the alkali component in the alkali developer. In addition, for the imidazole compound (B), it does not have a structure that causes interaction with the alkali component in the alkali developer. Therefore, the bismaleimide compound (A) and the imidazole compound (B) are in the alkali developer, for example, in a state of maintaining the structure of other components such as the compound (C) compounded as needed, along with the dissolution in the alkali developer, can be dissolved in the alkali developer. Therefore, it is inferred that in the development process, even if the alkali developer flows into the unexposed part (resin composition), the bismaleimide compound (A) and the imidazole compound (B) will not hinder the components that react with the alkali component in the alkali developer, and the resin composition has excellent alkali developability.

[0074] Furthermore, usually, when a printed circuit board is manufactured, in order to improve the adhesion between the conductor layer and the insulating layer, an adhesive metal such as titanium is inserted between the conductor layer (copper film) and the insulating layer. However, when there are insufficient functional groups with adhesive properties to metals such as titanium on the surface of the insulating layer, even if an adhesive metal such as titanium is inserted between the conductor layer and the insulating layer, the cured insulating layer cannot obtain sufficient adhesion to the adhesive metals such as titanium. Therefore, if the insulating layer is exposed to high temperature in a hygroscopic state or in a reflow soldering process, the adhesion strength between the conductor layer and the insulating layer is significantly reduced, and there is a worry about peeling. On the other hand, by making the resin composition include maleimide compound (A) and imidazole compound (B), the insulating layer obtained has excellent adhesion to the adhesive metals such as titanium. The reason is still uncertain, but the inventors speculate as follows.

[0075] That is, imidazole compound (B) as mentioned above, does not participate in photo-radical reaction, does not react with bismaleimide compound (A). Therefore, in the cured product (insulating layer) after the photocuring based on bismaleimide compound (A), imidazole compound (B) can also exist under the state of maintaining its structure. Moreover, imidazole compound (B) together with specific functional group, because the total of carbon number contained in functional group is more than 8, volume is large, therefore even if the compound with carboxyl group is included in resin composition, it is not easy to form salt, can exist under the state of maintaining its structure until inserting the metal of adhesiveness such as titanium. Imidazole compound is excellent in adhesion to metal, therefore, insulating layer can obtain sufficient adhesion to the metal of adhesiveness such as titanium, and it is inferred that the insulating layer can maintain the excellent adhesion strength with the conductor layer even if it is exposed to high temperature in the hygroscopic state, in the reflow process, etc.

[0076] Based on the above, the resin composition of the present embodiment does not hinder the photocuring reaction in the exposure process of the production of the multilayer printed circuit board, has excellent photocurability to various active energy rays, can be given excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to adhesive metals such as titanium. In addition, the heat resistance, insulation reliability, and thermal stability of the obtained cured product are also excellent. Therefore, according to the present embodiment, the protective film and the insulating layer in the multilayer printed circuit board and the semiconductor device can be appropriately formed, and a high-density printed circuit board and a semiconductor device with a high-precision pattern can be obtained.

[0077] The bismaleimide compound (A) is not particularly limited as long as the effects of the present invention are exhibited, but the mass average molecular weight is preferably 100 to 5000, more preferably 300 to 4500, from the viewpoint of obtaining an appropriate viscosity and suppressing an increase in the viscosity of the varnish.

[0078] Next, the structure of the bismaleimide compound (A) is described.

[0079] In the formula (1) of the bismaleimide compound (A), R1 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. R1 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoint of obtaining an appropriate viscosity and being able to control the increase in the viscosity of the varnish.

[0080] The carbon number of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0081] Examples of the linear or branched alkylene group 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.

[0082] The number of carbon atoms in the alkenylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0083] Examples of the linear or branched alkenylene group include vinylene, 1-methylvinylene, arylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene.

[0084] 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, and more preferably a linear alkylene group, from the viewpoint of obtaining a more appropriate viscosity and being able to further control the increase in viscosity of the varnish.

[0085] The carbon number of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0086] As the linear or branched alkylene group, the above-mentioned R1 can be referred to.

[0087] The number of carbon atoms in the alkenylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0088] As the linear or branched alkenylene group, the above-mentioned R1 can be referred to.

[0089] In the formula (1), R1 and R2 may be the same or different, and are preferably the same from the viewpoint of being able to more easily synthesize the bismaleimide compound (A).

[0090] In formula (1), R3 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. R3 each independently preferably represents a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms, from the perspective of obtaining a more appropriate viscosity and being able to further control the viscosity increase of the varnish, more preferably 1 to 5 groups (R3) in R3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms, and further preferably 1 to 3 groups (R3) in R3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms.

[0091] The number of carbon atoms in the alkyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0092] Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

[0093] The number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish.

[0094] Examples of the linear or branched alkenyl group include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl.

[0095] In the formula (1), n1 each independently represents an integer of 1 to 10.

[0096] The bismaleimide compound (A) has a maleimide group at both ends of the molecular chain. Both ends refer to the two ends in the molecular chain of the bismaleimide compound (A). For example, when the constituent unit shown in formula (1) is at the end of the molecular chain of the bismaleimide compound (A), it means that there is a maleimide group at the end of the molecular chain of R1, or at the end of the molecular chain of the N atom of the maleimide ring, or at both ends. The bismaleimide compound (A) may also have a maleimide group other than the two ends of the molecular chain.

[0097] The maleimide group is represented by formula (11), and the N atom is bonded to the molecular chain of the bismaleimide compound (A). The maleimide groups bonded to the bismaleimide compound (A) may all be the same or different, and preferably the maleimide groups at both ends of the molecular chain are the same.

[0098]

[0099] In formula (11), R 21 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. From the perspective of more suitable photocuring, it is preferred that the two R 21 All are hydrogen atoms.

[0100] The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of more appropriately performing photocuring.

[0101] As the linear or branched alkyl group, refer to the above-mentioned R3.

[0102] Examples of such bismaleimide compounds (A) include maleimide compounds represented by formula (12). These may be used alone or in combination of two or more.

[0103]

[0104] In formula (12), a represents an integer of 1 to 10. From the viewpoint of obtaining a more appropriate viscosity and being able to more appropriately control the increase in viscosity of the varnish, a is preferably an integer of 1 to 6.

[0105] A commercially available bismaleimide compound (A) may be used. Examples of the commercially available bismaleimide compound include MIZ-001 (trade name, maleimide compound containing the formula (12)) manufactured by Nippon Kayaku Co., Ltd.

[0106] In the resin composition, the content of the bismaleimide compound (A) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, further preferably 40 to 75 parts by mass, further more preferably 50 to 70 parts by mass, and further preferably 55 to 65 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of obtaining a cured product with the bismaleimide compound as the main component, further improving the photocurability, and obtaining more excellent heat resistance and thermal stability.

[0107] In addition, when the resin composition contains a bismaleimide compound (A) and a maleimide compound (D) other than the bismaleimide compound (A), the content of the bismaleimide compound (A) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, further preferably 40 to 75 parts by mass, further more preferably 50 to 70 parts by mass, and further preferably 55 to 65 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (D), from the viewpoint of obtaining a cured product containing the bismaleimide compound as a main component, further improving photocurability, and obtaining more excellent heat resistance and thermal stability. The maleimide compound (D) preferably comprises at least one selected from the group consisting of the compound represented by formula (5), the compound represented by formula (6), the compound represented by formula (7), the compound represented by formula (8), the compound represented by formula (9), and the compound represented by formula (10), more preferably comprises at least one selected from the group consisting of the compound represented by formula (5), the compound represented by formula (6), and the compound represented by formula (7), and further preferably comprises at least one selected from the group consisting of the compound represented by formula (5) and the compound represented by formula (6).

[0108] In the case where the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) together with a compound (C), a compound (D), and an initiator (E), the content of the bismaleimide compound (A) is preferably 10 to 85 parts by mass, more preferably 15 to 80 parts by mass, further preferably 30 to 70 parts by mass, and further preferably 40 to 60 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint of being able to impart more excellent alkali developability, not inhibiting the photocuring initiator in the resin composition, and being able to exhibit better curing properties.

[0109] The bismaleimide compound (A) can be used alone or in combination of two or more.

[0110] (Method for producing bismaleimide compound (A))

[0111] The bismaleimide compound (A) can be produced by a known method. For example, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a monomer containing a diamine including a dimer diamine, and maleic anhydride can be subjected to a polyaddition reaction at a temperature of usually about 80 to 250° C., preferably about 100 to 200° C., usually for about 0.5 to 50 hours, preferably about 1 to 20 hours to obtain an addition polymer. Thereafter, the addition polymer is subjected to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of usually about 60 to 120° C., preferably about 80 to 100° C., usually for about 0.1 to 2 hours, preferably about 0.1 to 0.5 hours, to obtain a bismaleimide compound (A).

[0112] Dimer diamines are obtained, for example, by reductive amination of dimer acid, and the amination reaction can be carried out, for example, by known methods such as reduction using ammonia and a catalyst (for example, the method described in Japanese Patent Publication No. 9-12712). Dimer acid refers to a dibasic acid obtained by dimerizing unsaturated fatty acids through intermolecular polymerization reactions. Depending on the synthesis conditions and purification conditions, it usually contains a small amount of monomeric acid, trimer acid, etc. in addition to dimer acid. Double bonds will remain in the molecules obtained after the reaction, but in this embodiment, the double bonds present in the molecules are reduced by hydrogenation reaction to become saturated dibasic acids, which are also included in dimer acid. Dimer acid can be obtained, for example, by using Lewis acid and Bronsted acid as catalysts to polymerize unsaturated fatty acids. Dimer acid can be manufactured by known methods (for example, the method described in Japanese Patent Publication No. 9-12712). Examples of the unsaturated fatty acid include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, 5Z,8Z,10E,12E,14Z-eicosapentaenoic acid, osbond acid, clupanodonic acid, tetracosapentaenoic acid, docosahexaenoic acid, and nisinic acid. The number of carbon atoms in the unsaturated fatty acid is usually 4 to 24, preferably 14 to 20.

[0113] In the production of the bismaleimide compound (A), a monomer containing a diamine is preferably dissolved or dispersed in an organic solvent in an inert atmosphere such as argon or nitrogen in advance to form a slurry, thereby preparing a monomer solution containing a diamine. Then, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferably dissolved or dispersed in an organic solvent to form a slurry or added in a solid state to the monomer solution containing a diamine.

[0114] By adjusting the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the number of moles of the total amount of the monomer including the diamine and the maleimide compound, any bismaleimide compound (A) can be obtained.

[0115] Various known solvents can be used in the addition polymerization 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; and aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol, and propanol. ; phenols containing aromatic groups such as phenol and cresol; alcohols containing aromatic groups such as benzyl alcohol; glycols such as ethylene glycol and propylene glycol, or monoethers or diethers of these glycols and methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of these monoethers such as glycol ethers; cyclic ethers such as dioxane and tetrahydrofuran; carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as dimethyl sulfoxide. These solvents can be used alone or in combination of two or more as needed.

[0116] In addition, in the imidization reaction, a catalyst is preferably used. As the catalyst, for example, a tertiary amine and a dehydration catalyst can be used. As the tertiary amine, a heterocyclic tertiary amine is preferred, for example, pyridine, picoline, quinoline, and isoquinoline can be mentioned. As the dehydration catalyst, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride can be mentioned.

[0117] The amount of the catalyst added is preferably about 0.5 to 5.0 times the molar equivalent of the imidization agent relative to the amide group, and 0.5 to 10.0 times the molar equivalent of the dehydration catalyst relative to the amide group.

[0118] After the imidization reaction is completed, the solution can be used as a bismaleimide compound (A) solution, or a poor solvent can be added to the reaction solvent to make the bismaleimide compound (A) into a solid material. As the poor solvent, for example, water, methanol, ethanol, 2-propanol, ethylene glycol, triethylene glycol, 2-butanol, 2-pentanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol and tert-butyl alcohol can be cited.

[0119] [Imidazole compound (B)]

[0120] The resin composition of the present embodiment contains an imidazole compound (B) represented by formula (2). The compound (B) can be used alone or in combination of two or more.

[0121]

[0122] In formula (2), R4 to R7 each independently represent a hydrogen atom, an aldehyde group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and the total number of carbon atoms of R4 to R7 is 8 or more.

[0123] As mentioned above, compound (B) does not hinder light transmittance, does not participate in photoradical reaction, and does not react with bismaleimide compound (A). Therefore, in the exposure process of making a multilayer printed circuit board, it does not hinder the photocuring reaction, and a cured product can be appropriately obtained using various active energy rays.

[0124] In addition, the compound (B) does not have a structure that causes interaction with the alkali component in the alkali developer. Therefore, in the development step, a resin composition containing both the bismaleimide compound (A) and the compound (B) can be obtained, and after exposure, the resin composition of the unexposed portion can be given excellent alkali developability.

[0125] Furthermore, compound (B) has a specific functional group, and the total number of carbon atoms contained in the functional group is more than 8, and the volume is large, so in the cured product (insulating layer) after light curing, until the metal with adhesive properties such as titanium is inserted, it can exist in a state of maintaining its structure. Moreover, as mentioned above, the imidazole compound has excellent adhesion to metals, so the insulating layer obtained can obtain sufficient adhesion to adhesive metals such as titanium. Therefore, even if the insulating layer is exposed to high temperatures in a hygroscopic state or in a reflow process, it is possible to maintain excellent adhesion strength with the conductor layer.

[0126] For compound (B), a chloroform or N-methylpyrrolidone solution containing it at 1% by mass is prepared, and when the transmittance of the chloroform or N-methylpyrrolidone solution containing compound (B) at 1% by mass is measured using active energy rays containing a wavelength of 365nm (i-ray), its transmittance is preferably 5% or more. When it is this compound (B), very excellent light transmittance is exhibited. In addition, when the transmittance of the chloroform or N-methylpyrrolidone solution containing compound (B) at 1% by mass is measured using active energy rays containing a wavelength of 405nm (h-ray), its transmittance is preferably 5% or more. In this case, very excellent light transmittance is also exhibited. If such a compound (B) is used, for example, there is a tendency that when a printed circuit board with high density and high-precision wiring formation (pattern) is manufactured using a direct drawing exposure method, even when an active energy ray containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is effectively caused. For the transmittance of wavelength 365nm (i-ray), from the aspect of being able to obtain a resin composition with better photocurability, 1% or more, 2% or more, 3% or more, 4% or more, and 5% or more are preferred ranges in order. For the transmittance of wavelength 405nm (h-ray), from the aspect of being able to obtain a resin composition with better photocurability, 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more are preferred ranges in order. It should be noted that the upper limit of the transmittance of wavelength 365nm (i-ray) and the transmittance of wavelength 405nm (h-ray) is, for example, less than 99.9%.

[0127] Next, the structure of the imidazole compound (B) is described.

[0128] In the formula (2) of the imidazole compound (B), R4 to R7 each independently represent a hydrogen atom, an aldehyde group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0129] Examples of the aldehyde group include a formyl group, a -R 23 -CHO. 23For example, a straight-chain or branched hydrocarbon group having a total carbon number of 1 to 20 can be cited. It should be noted that * represents an atomic bond with any group in R4 to R7. The hydrocarbon group may have a substituent. Such a substituent is not particularly limited, and for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom, etc.), a hydroxyl group, a cyano group, a nitro group, a mercapto group, a heterocyclic group, a straight-chain aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkanoyloxy group, an aroyloxy group, and an alkylsilyl group can be cited. It should be noted that as a substituent, it is preferred that a carboxyl group is not contained. As an aldehyde group, formyl is preferred from the aspect of obtaining better compatibility.

[0130] As an alkyl group having 1 to 20 carbon atoms and optionally having a substituent, for example, a linear or branched alkyl group having 1 to 20 carbon atoms and optionally having a substituent can be mentioned. As such an alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, a p-tert-butylcyclohexyl group, an n-decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group can be mentioned. The hydrocarbon group can have a substituent, and as a substituent, the above can be referred to. Among them, from the aspect of obtaining a better light transmittance, it is preferred that R4 to R7 contain an alkyl group having at least 8 carbon atoms, more preferably contain an alkyl group having 10 to 20 carbon atoms, and further preferably contain an alkyl group having 11 to 18 carbon atoms. In addition, from the perspective of not participating in the photo-radical reaction and being able to keep the structure longer in the cured product, it is preferred that no substituent is included. In the case of containing substituents, from the perspective of not participating in the photo-radical reaction, it is preferred that the substituent contains a halogen atom, a hydroxyl group, a cyano group, and an aryl group. As the halogen atom in the substituent, a fluorine atom and a chlorine atom are more preferred. As the aryl group in the substituent, a phenyl group is more preferred. In addition, from the perspective of not easily forming a salt with a carboxylic acid and obtaining a bulkier structure, it is preferred that at least a phenylmethyl group and a phenylethyl group are included in R4 to R7.

[0131] As an aromatic group having 6 to 20 carbon atoms which may optionally have a substituent, for example, phenyl, naphthyl, biphenyl, terphenyl, phenanthrenyl, anthracenyl, etc. can be cited. As a substituent, reference can be made to the above. Among them, from the aspect of obtaining a better light transmittance, it is preferred that at least phenyl is included in R4 to R7. In addition, from the aspect of not participating in the photo-radical reaction and being able to keep the structure longer in the cured product, it is preferred that no substituent is included. In the case of containing a substituent, from the aspect of not participating in the photo-radical reaction, as a substituent, a halogen atom, a hydroxyl group, a cyano group, a straight-chain aliphatic hydrocarbon group, and a branched aliphatic hydrocarbon group are preferably included. As an aromatic group among the substituents, a phenyl group is more preferred. As a branched aliphatic hydrocarbon group among the substituents, an isopropyl group is more preferred.

[0132] As R4 to R7, from the perspective of obtaining better light transmittance, not participating in photo-free radical reaction, and being able to keep the structure longer in the cured product, it is preferred that at least undecyl, ethyl cyano, and phenyl are included. It is preferred that any group among R4 to R7 includes undecyl, and any group among R4 to R7 includes ethyl cyano, that is, it is preferred that any group among R4 to R7 includes undecyl and ethyl cyano. It is preferred that the three groups selected from R4 to R7 each have a phenyl.

[0133] In the formula (2) of the imidazole compound (B), the total number of carbon atoms of R4 to R7 is 8 or more. In the present specification, when the number of carbon atoms is counted, for example, when R4 to R7 include an aldehyde group (-CHO) or a cyano group (CN), the carbon atoms included in these groups are also counted in the carbon number. That is, when R4 to R7 include a formyl group, the carbon number of the formyl group is counted as 1. In the case of a methylcyano group (-CH2CN), its carbon number is 2. In addition, when a substituent in R4 to R7 includes a carbon atom, its carbon number is also counted. That is, in the case of diisopropylphenyl, its carbon number is 12, and in the case of cyanophenyl, its carbon number is 7. On the other hand, the carbon atoms of the imidazole ring are not counted. That is, when R4 to R7 include a hydrogen atom, the carbon number of the imidazole ring bonded to the hydrogen atom is not counted, and in this case, the carbon number is 0. That is, in the present specification, the total number of carbon atoms of imidazole in which R4 to R7 are all hydrogen atoms is 0.

[0134] The total number of carbon atoms in R4 to R7 is preferably 10 to 20, more preferably 11 to 18, from the viewpoint of maintaining light transmittance that does not inhibit photocuring and being less likely to participate in the reaction to obtain a bulkier structure.

[0135] The imidazole compound (B) is preferably selected from the group consisting of 2-undecyl imidazole, 2-heptadecylimidazole, 1-(triphenylmethyl)imidazole, 1-(2,6-diisopropylphenyl)imidazole, 1-(10-hydroxydecyl)imidazole, 1-(2-phenylethyl)-1H-imidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-benzyl-2-methylimidazole, 2,4-diphenyl-1H-imidazole, 4,5- At least one selected from the group consisting of 2-undecyl imidazole, 1-trityl imidazole-4-carboxaldehyde, 2,4,5-triphenyl imidazole, 2-(4-hydroxyphenyl)-4,5-diphenyl imidazole, 2-(4-fluorophenyl)-4,5-diphenyl imidazole, 2-(2-chlorophenyl)-4,5-diphenyl imidazole, 2-(4-chlorophenyl)-4,5-diphenyl imidazole, 4,5-bis(hydroxymethyl)-2-phenyl imidazole, and 4-(4,5-diphenyl-1H-imidazol-2-yl)benzonitrile. Among them, as the imidazole compound (B), it is more preferred to include at least one selected from the group consisting of 2-undecyl imidazole, 1-(2-cyanoethyl)-2-undecyl imidazole, and 2,4,5-triphenyl imidazole from the viewpoint of further improving the adhesion to an adhesive metal such as titanium.

[0136] The content of the imidazole compound (B) in the resin composition 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 of the resin solid content in the resin composition, from the viewpoint that the insulating layer has more sufficient adhesion with an adhesive metal such as titanium, the insulating layer can maintain a better adhesion strength with the conductor layer even when it is in a hygroscopic state and exposed to a high temperature in a reflow process, etc., and thus does not hinder photocurability.

[0137] In addition, when the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) and also contains a compound (C), a compound (D), and an initiator (E), the content of the imidazole compound (B) is preferably 0.1 to 20 parts by mass, more preferably 0.15 to 15 parts by mass, further preferably 0.2 to 10 parts by mass, and further more preferably 0.3 to 7.0 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint that the insulating layer has more sufficient adhesion to an adhesive metal such as titanium, the insulating layer can maintain a more excellent adhesion strength with the conductor layer even when exposed to high temperature in a reflow process or the like in a hygroscopic state, and does not inhibit photocurability.

[0138] [Compounds containing one or more carboxyl groups (C)]

[0139] The resin composition of the present embodiment preferably also includes a compound (C) containing more than one carboxyl group. As long as the compound (C) contains more than one carboxyl group in the compound, it is not particularly limited. The carboxyl group can be a salt such as a sodium salt and a potassium salt. When the molecule contains more than two carboxyl groups, it can also be an acid anhydride formed by connecting them to each other. The compound (C) can be used alone or in combination with two or more.

[0140] In the present embodiment, in the exposure process of the production of a multilayer printed circuit board, a resin composition comprising a compound (C) and a maleimide compound (D) and a photocuring initiator (E) mixed as needed while comprising a bismaleimide compound (A) and an imidazole compound (B) is used, so as not to hinder the photocuring reaction, and a cured product can be appropriately obtained using various active energy rays. In addition, in the developing process, a resin composition comprising a compound (C) and a maleimide compound (D) and a photocuring initiator (E) mixed as needed while comprising a bismaleimide compound (A) and an imidazole compound (B) can be obtained, and after exposure, excellent alkali developability can be given to the resin composition of the unexposed portion. The reason is still uncertain, but the inventors speculate as follows.

[0141] That is, in the exposure process of making a multilayer printed circuit board, the compound (C) does not have a functional group that participates in the photocuring reaction of the exposure process and does not hinder the photocuring reaction. The bismaleimide compound (A) and the imidazole compound (B) do not have a skeleton that hinders light transmittance, but have very excellent light transmittance. Therefore, even if the bismaleimide compound (A) and the imidazole compound (B) are included while also containing the compound (C) and the compound (D) and the initiator (E) mixed as needed, photopolymerization will proceed and a cured product can be appropriately obtained.

[0142] Moreover, the compound (C) may be present in the resin composition of the unexposed portion. Therefore, in the development process, when the alkaline developer flows into the unexposed portion, the alkaline component in the alkaline developer and the carboxyl group in the compound (C) can appropriately form a salt, and the water solubility is improved, thereby obtaining excellent alkaline developability.

[0143] For compound (C), an N-methylpyrrolidone solution containing it at 1% by mass is prepared, and when the transmittance of the N-methylpyrrolidone solution containing compound (C) at 1% by mass is measured using active energy rays containing a wavelength of 365nm (i-ray), its transmittance is preferably 5% or more. Such a compound (C) exhibits very excellent light transmittance. In addition, when the transmittance of an N-methylpyrrolidone solution containing compound (C) at 1% by mass is measured using active energy rays containing a wavelength of 405nm (h-ray), its transmittance is 5% or more. In this case, very excellent light transmittance is also exhibited. If such a compound (C) is used, for example, when a printed circuit board with high density and high-precision wiring formation (pattern) is manufactured using a direct drawing exposure method, even when an active energy ray containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is effectively induced. For the transmittance of a wavelength of 365nm (i-ray), from the perspective of being able to obtain a resin composition with better photocurability, 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more are preferred ranges in order. For the transmittance of a wavelength of 405nm (h-ray), from the perspective of being able to obtain a resin composition with better photocurability, 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more are preferred ranges in order. It should be noted that the upper limit of the transmittance of a wavelength of 365nm (i-ray) and the transmittance of a wavelength of 405nm (h-ray) is, for example, less than 99.9%.

[0144] In the present embodiment, from the viewpoint of obtaining more excellent alkali developability, the compound (C) preferably contains an integer of 2 to 20 carboxyl groups in the molecule.

[0145] The molecular weight of the compound (C) is preferably 50 to 10,000, more preferably 100 to 8,000, further preferably 130 to 6,000, and still further preferably 150 to 5,000 from the viewpoint of further improving developability.

[0146] The mass average molecular weight of the compound (C) is preferably 50 to 10,000, more preferably 100 to 8,000, and even more preferably 150 to 5,000 from the viewpoint of further improving developability.

[0147] The content of the compound (C) in the resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, further preferably 1.0 to 15 parts by mass, further preferably 1.5 to 10 parts by mass, and further preferably 2.0 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, from the perspective of being able to impart more excellent alkali developability, not inhibiting the photocuring reaction in the resin composition, and being able to exhibit good curing properties.

[0148] When the resin composition contains a bismaleimide compound (A), a compound (B) and a compound (C) and also contains a compound (D) and an initiator (E), the content of the compound (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, further preferably 1.0 to 10 parts by mass, and further more preferably 1.5 to 5.0 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint of being able to impart more excellent alkali developability, not inhibiting the photocuring reaction in the resin composition, and being able to exhibit good curing properties.

[0149] Examples of the compound (C) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, heteroatom compounds containing one or more carboxyl groups, and acid anhydrides. These compounds (C) may be used alone or in combination of two or more.

[0150] (Aliphatic compounds containing one or more carboxyl groups)

[0151] As the aliphatic compound containing more than one carboxyl group, for example, chain aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, chain aliphatic polycarboxylic acid, and alicyclic polycarboxylic acid can be cited. These compounds can have substituents such as hydrogen atoms, alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl in the molecule. In addition, when these compounds have more than two carboxyl groups in the molecule, they can also be acid anhydrides formed by connecting them to each other. When these compounds have carboxylalkyl in the molecule, they can also be acid anhydrides formed by connecting carboxylalkyl and carboxyl. When these compounds have more than two carboxylalkyl in the molecule, they can also be acid anhydrides formed by connecting them to each other.

[0152] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

[0153] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexyloxy group, and a 2-methylpropoxy group.

[0154] Examples of the aryloxy group include a phenoxy group and a p-tolyloxy group.

[0155] Examples of the aryl group include a phenyl group, a tolyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

[0156] Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, and an aminononyl group.

[0157] Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, and a carboxynonyl group.

[0158] Examples of the chain aliphatic monocarboxylic acid include saturated fatty acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid, and unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, linolenic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

[0159] Examples of the alicyclic monocarboxylic acid include monocyclic carboxylic acids such as cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid; and polycyclic or bridged alicyclic carboxylic acids such as norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid, ethyladamantanecarboxylic acid, and butyladamantanecarboxylic acid.

[0160] Examples of the chain aliphatic polycarboxylic acid include carboxylic acids obtained by adding one or more carboxyl groups to a chain aliphatic monocarboxylic acid, such as malonic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

[0161] Examples of the alicyclic polycarboxylic acid include carboxylic acids obtained by further adding one or more carboxyl groups to an alicyclic monocarboxylic acid. For example, monocyclic carboxylic acids such as cyclopropanedicarboxylic acid, cyclopropylenedicarboxylic acid, cyclopropylenetricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutenetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopentenetricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentenetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexanetricarboxylic acid, cyclohexenetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexenetetracarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexenepentacarboxylic acid, cyclohexanehexacarboxylic acid, cyclohexenehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptenedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclooctenedicarboxylic acid, and polycyclic or bridged alicyclic dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid may be mentioned.

[0162] (Aromatic compounds containing one or more carboxyl groups)

[0163] As the parent skeleton of the aromatic compound containing more than one carboxyl group, for example, benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxylbenzene, hexacarboxylbenzene, naphthalenecarboxylic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, anthracene pentacarboxylic acid, etc. can be cited. Aromatic compounds can have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl on the aromatic rings of these parent skeletons. In addition, when these compounds have more than two carboxyl groups in the molecule, they can be optionally connected to form anhydrides. When these compounds have carboxyl alkyl in the molecule, they can be connected to form anhydrides with carboxyl groups. When these compounds have more than two carboxyl alkyl in the molecule, they can be optionally connected to form anhydrides. For these substituents, reference can be made to the above.

[0164] (Heteroatom compounds containing one or more carboxyl groups)

[0165] As the parent skeleton of the heteroatom compound containing more than one carboxyl group, for example, compounds containing more than one carboxyl group on heterocycles such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole can be cited. The heteroatom compound can have, for example, hydrogen atoms, and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl on these parent skeletons. In addition, when these compounds have more than two carboxyl groups in the molecule, they can be optionally connected to form anhydrides. When these compounds have carboxylalkyl in the molecule, they can be connected to form anhydrides. When these compounds have more than two carboxylalkyl in the molecule, they can be connected to form anhydrides. When these compounds have more than two carboxylalkyl in the molecule, they can be connected to form anhydrides. For these substituents, reference can be made to the above description.

[0166] The compound (C) preferably contains a compound represented by formula (3) because it has better compatibility with the bismaleimide compound (A) and the imidazole compound (B), can quickly and appropriately form a salt with the alkali component in the alkali developer, and has a further improved water solubility.

[0167]

[0168] In formula (3), R8 each independently represents a group represented by formula (4) or a hydrogen atom. R9 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. At least one R8 is a group represented by formula (4).

[0169]

[0170] In the formula (4), -* represents an atomic bond to the oxygen atom (O) directly connected to R8 in the formula (3).

[0171] In formula (3), for R8, from the perspective of being able to impart better alkali developability, it is preferred that two or more groups represented by formula (4) are included, more preferably three or more groups represented by formula (4) are included, and it is further preferred that all R8 are groups represented by formula (4). For the group represented by formula (4), when the position of the carbonyl group is set to the 1st position relative to the cyclohexane ring, as long as the carboxyl group is bonded to the 2nd position relative to the carbonyl group, the other carboxyl group can be bonded to any position from the 3rd to the 6th position of the cyclohexane ring. In addition, the compound represented by formula (3) exists in the form of a cis-isomer, a trans-isomer, and a mixture of a cis-isomer and a trans-isomer because the structure of the carbonyl group bonded to the cyclohexane ring in the group represented by formula (4) has a stereostructure. That is, the compound represented by formula (3) may be a single isomer or a mixture containing two or more isomers.

[0172] In formula (3), for R8, from the perspective of being able to impart better alkali developability, it is preferred that at least one R8 is a group represented by formula (13). That is, it is preferred that in the group represented by formula (13), the stereostructure of the carbonyl group at position 1 and the carboxyl group at position 2 bonded to the cyclohexane ring is a cis isomer. Regarding the other carboxyl group, its stereostructure may be a cis isomer or a trans isomer. For R8, from the perspective of being able to further impart better alkali developability, it is preferred that two or more groups represented by formula (13) are included, more preferably three or more groups represented by formula (13) are included, and it is further preferred that all R8 are groups represented by formula (13). It is not certain that at least one R8 is a group represented by formula (13) that can impart better alkali developability, but the present inventors speculate as follows. That is, if the carbonyl group bonded to position 1 and the carboxyl group bonded to position 2 are cis isomers, a stereostructure in which the carboxyl group at position 2 and the alkali component in the alkali developer are more likely to form a salt can be obtained in the resin composition. Therefore, it is presumed that the water solubility is further improved, and the inflow of the alkali developer into the resin composition is further promoted.

[0173]

[0174] In the formula (13), -* represents an atomic bond to the oxygen atom (O) directly connected to R8 in the formula (3).

[0175] In the formula (3), R9 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

[0176] Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl.

[0177] From the viewpoint of exhibiting better solubility in a solvent, R9 is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group, and still more preferably a methyl group, an ethyl group, and an n-propyl group.

[0178] The compound represented by formula (3) is preferably a compound represented by formula (14) or a compound represented by formula (15), and more preferably a compound represented by formula (15), from the viewpoint of being able to impart more excellent alkali developability and further exhibiting better solubility in a solvent.

[0179]

[0180] The content of the compound represented by formula (3) in the resin composition is preferably 10 to 100 parts by mass, more preferably 30 to 99 parts by mass, further preferably 50 to 95 parts by mass, further more preferably 60 to 93 parts by mass, and further preferably 80 to 90 parts by mass relative to 100 parts by mass of the total of the compound (C), from the perspective of being able to impart more excellent alkali developability, not inhibiting the photocuring reaction in the resin composition, and being able to exhibit better curing properties.

[0181] [Method for producing the compound represented by formula (3)]

[0182] The compound represented by formula (3) can be manufactured by a known method, for example, it can be obtained by a process including subjecting the alcohol compound represented by formula (16) to an esterification reaction with the acid anhydride represented by formula (17) (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride). It should be noted that the acid anhydride represented by formula (17) has a stereostructure due to the structure of two carbonyl groups and one carboxyl group bonded to the cyclohexane ring, and therefore exists in the form of a cis-isomer, a trans-isomer, and a mixture of a cis-isomer and a trans-isomer. That is, the acid anhydride represented by formula (17) can be a single species, or can also be a mixture containing two or more isomers.

[0183]

[0184] In formula (16), R 22 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

[0185] As the linear or branched alkyl group having 1 to 6 carbon atoms, including preferred embodiments thereof, reference may be made to R9 in the above-mentioned formula (3).

[0186]

[0187] Examples of the alcohol compound represented by formula (17) include di(trihydroxymethyl)ethane, di(trihydroxymethyl)propane, di(trihydroxymethyl)butane, di(trihydroxymethyl)pentane, 2,2'-(oxybis(methylene))bis(propane-1,3-diol), 2,2'-(oxybis(methylene))bis(2-methylpropane-1,3-diol), and 2-((2,2-bis(hydroxymethyl)butoxy)methyl)-2-methylpropane-1,3-diol.

[0188] As the acid anhydride represented by formula (17), it is preferred to include the acid anhydride represented by formula (18) (cis, cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride) from the aspect of being able to impart more excellent alkali developability when a cured product is produced using the compound represented by formula (3). That is, in the acid anhydride represented by formula (18), when the position of the carbonyl group is set to the 1st position and the 2nd position relative to the cyclohexane ring, the stereostructure of the carbonyl group bonded to the 4th position relative to the carbonyl group and the two carbonyl groups is preferably a cis isomer.

[0189]

[0190] The esterification reaction may be carried out in a solvent or in the absence of a solvent. The solvent is not particularly limited as long as it is a solvent that does not react with the alcohol compound and the acid anhydride.

[0191] As such solvents, for example, halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0192] Among these, halogen-containing solvents, aprotic polar solvents, ketone solvents, and ester solvents are preferred because they can sufficiently dissolve the alcohol compound and the acid anhydride.

[0193] As the halogen-containing solvent, dichloromethane is preferred. As the aprotic polar solvent, dimethylacetamide is preferred. As the ketone solvent, methyl ethyl ketone is preferred. As the cellosolve solvent, propylene glycol monomethyl ether is preferred. As the ester solvent, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred.

[0194] When a solvent is used, the amount used is usually 20 to 2000 parts by mass based on 100 parts by mass of the total of the alcohol compound and the acid anhydride.

[0195] The esterification reaction can be carried out without a catalyst or with a catalyst.

[0196] When a catalyst is used, examples of the catalyst include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic 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; pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazoles; , triazole, and tetrazole and other heterocyclic compounds; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, and trioctylmethylammonium acetate and other quaternary ammonium salts; orthotitanic acids such as tetraethyl orthotitanate and tetramethyl orthotitanate; metal soaps such as tin octanoate, cobalt octanoate, zinc octanoate, manganese octanoate, calcium octanoate, sodium octanoate, and potassium octanoate. These catalysts can be used alone or in combination of two or more. Among these, from the aspect of good reactivity, amine compounds, aliphatic amines having an aromatic ring, and heterocyclic compounds are preferred, and triethylamine and 4-dimethylaminopyridine are more preferred. When a catalyst is used, the amount used is usually 0.0001 to 1000 parts by mass based on 1 part by mass of the alcohol compound.

[0197] Examples of the method for adding the catalyst include a method of directly adding the catalyst to the alcohol compound and / or the acid anhydride, and a method of adding a solution obtained by dissolving the catalyst in a soluble solvent to the alcohol compound, the acid anhydride, and / or a solvent containing the catalyst.

[0198] When the esterification is carried out using a catalyst, the reaction temperature of the esterification varies depending on the amount of the catalyst and the solvent used, and is not particularly limited, but is usually -20 to 150° C. In addition, 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.

[0199] In the present embodiment, the alcohol compound shown in formula (16) has a relatively high reactivity with the anhydride shown in formula (17), so esterification can be performed even in the absence of a catalyst. As the anhydride shown in formula (17), from the perspective of higher reactivity with the alcohol compound, it is preferred to include the anhydride shown in formula (18). In this specification, catalyst-free refers to not adding or only adding a very small amount of a catalyst that contributes to the esterification reaction. Specifically, it means that in the reaction, relative to 1 mass part of the alcohol compound shown in formula (16), the catalyst is made to be less than 50ppm. In addition, in the reaction, the catalyst that contributes to the esterification reaction is preferably 0ppm.

[0200] In the case of esterification without a catalyst, as a solvent, halogen-containing solvents, ketone solvents, and ester solvents are preferred from the perspective of being able to fully dissolve the alcohol compound and the acid anhydride and the obtained compound represented by formula (3) can also be fully dissolved. In addition, from the perspective of being able to show better solubility and being able to inhibit the hydrolysis of the acid anhydride, halogen-containing solvents and ester solvents are more preferred. Furthermore, from the perspective of being able to make the alcohol compound and the acid anhydride react well, being able to inhibit the hydrolysis of the acid anhydride and achieving a reduction in environmental burden, ester solvents are further preferred. As a halogen-containing solvent, dichloromethane is preferred from the perspective of being able to show better solubility. As a ketone solvent, methyl ethyl ketone is preferred from the perspective of being able to show better solubility. As an ester solvent, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred from the perspective of being able to show better solubility.

[0201] By using such a solvent without a catalyst, it is also possible to omit the step of isolating the compound represented by formula (3) from the reaction mixture described later and the purification step. It should be noted that the reaction temperature and reaction time are as described later.

[0202] The reason is still uncertain, but the present inventors speculate as follows. That is, by using a halogen-containing solvent, a ketone solvent, and an ester solvent, the hydrolysis of the acid anhydride represented by formula (17) can be appropriately suppressed, and side reactions other than the target esterification reaction can be suppressed. Therefore, it is speculated that impurities are less likely to be generated and a high-purity target product can be obtained.

[0203] The amount of the solvent used is usually 20 to 2000 parts by mass, preferably 20 to 1000 parts by mass, and more preferably 20 to 500 parts by mass, based on 100 parts by mass of the total of the alcohol compound and the acid anhydride, in order to further reduce the environmental burden.

[0204] When esterification is performed without a catalyst, the reaction temperature of the esterification can be appropriately set depending on the solvent used, and is usually -20 to 150°C, more preferably 0 to 150°C, and more preferably 20 to 120°C from the viewpoint of better esterification.

[0205] When the esterification is carried out without a catalyst, the reaction time is usually 0.5 to 100 hours, more preferably 0.5 to 80 hours, more preferably 0.5 to 50 hours from the perspective of suppressing side reactions and performing the esterification more satisfactorily. It should be noted that the reaction may be completed in one stage or may be carried out in two or more stages.

[0206] If an ester solvent is used as a solvent, the alcohol compound and the acid anhydride can be fully esterified without a catalyst, so the cost of the catalyst can be reduced, the process of removing the catalyst can be omitted, impurities are not easily generated, and a compound with higher purity can be obtained. Therefore, when it is this manufacturing condition, the process and purification process of separating the compound shown in formula (3) from the reaction mixture described later can also be saved. It should be noted that the reaction temperature and reaction time are as described above.

[0207] The reason for this is still unclear, but the present inventors speculate as follows. That is, the ester solvent can further inhibit the hydrolysis of the anhydride represented by formula (17), and can further inhibit side reactions other than the target esterification reaction. Therefore, it is speculated that compared with other solvents, it is less likely to produce impurities and can obtain a target product with higher purity.

[0208] For the method of separating the compound as the target from the reaction mixture containing the compound shown in formula (3), when the target is precipitated from the reaction solvent, it can be separated by filtration or centrifugation. In addition, when the target is dissolved in the reaction solvent, the solvent can be distilled off under reduced pressure, or a suitable poor solvent can be added to the reaction mixture, or the reaction mixture can be discharged into the poor solvent, etc. and precipitated, separated by filtration or centrifugation. It should be noted that as a poor solvent, for example, hydrocarbons such as hexane, heptane, cyclohexane, toluene, and xylene can be cited. These solvents can be used alone or in a suitable mixture of two or more.

[0209] When the separated compound needs to be further purified, it can be purified by a known method, such as distillation purification, recrystallization, column chromatography, sludge treatment, and activated carbon treatment.

[0210] The compound represented by the obtained formula (3) can be identified by known methods such as NMR (nuclear magnetic resonance analysis). The purity of the compound can be analyzed, for example, by GPC, liquid chromatography, and IR spectroscopy. Volatile components such as byproducts and residual solvents in the compound can be quantitatively analyzed, for example, by GPC and gas chromatography. The halogenide remaining in the compound can be identified, for example, by liquid chromatography-mass spectrometry, or by potentiometric titration using a silver nitrate solution or by ion chromatography after decomposition based on a combustion method.

[0211] In addition, in the present embodiment, as compound (C), from the aspect of being able to impart more excellent alkali developability to the resin composition, it is more preferred to include an acid anhydride of a fully hydrogenated aromatic polycarboxylic acid and / or a partially hydrogenated aromatic polycarboxylic acid. From the aspect of being able to impart more excellent alkali developability to the resin composition, it is further preferred to use these compounds together with the compound represented by formula (3).

[0212] Examples of the anhydrides of the fully hydrogenated aromatic polycarboxylic acids and the anhydrides of the partially hydrogenated aromatic polycarboxylic acids include anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride; 1,2,3-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, 3,3 The anhydrides of completely hydrogenated products or partially hydrogenated products thereof include ',4,4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, diphenylmethanetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, anthracenetetracarboxylic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, benzenepentacarboxylic acid, and benzenehexacarboxylic acid.

[0213] The anhydrides of fully hydrogenated aromatic polycarboxylic acids and the anhydrides of partially hydrogenated aromatic polycarboxylic acids preferably have alicyclic structures such as monocyclic cycloalkanes such as cyclopentane and cyclohexane; monocyclic cycloolefins such as cyclopropene and cyclohexene; bicyclic alkanes such as bicycloundecane and decalin; and bicyclic olefins such as norbornene and norbornadiene, and more preferably have monocyclic cycloalkanes or monocyclic cycloolefins, from the viewpoint of being able to impart more excellent alkali developability and having excellent compatibility with the compound represented by formula (3) when used together with the compound represented by formula (3). Examples of such preferred anhydrides include 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride. From the viewpoint of being able to impart more excellent alkali developability and having more excellent compatibility with the compound represented by formula (3) when used together with the compound represented by formula (3), 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is more preferred, and cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is more preferred.

[0214] In the resin composition, the total content of the fully hydrogenated product of the aromatic polycarboxylic acid and the anhydride of the partially hydrogenated product of the aromatic polycarboxylic acid is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 35 parts by mass, further preferably 1.0 to 30 parts by mass, further more preferably 5.0 to 25 parts by mass, and further preferably 10 to 20 parts by mass relative to 100 parts by mass of the total of the compound (C), from the viewpoint of being able to impart more excellent alkali developability, not inhibiting the photocuring reaction in the resin composition, and being able to exhibit better curability.

[0215] [Maleimide compound (D)]

[0216] The resin composition of the present embodiment preferably further contains at least one maleimide compound (D) selected from the group consisting of a compound represented by formula (5), a compound represented by formula (6), a compound represented by formula (7), a compound represented by formula (8), a compound represented by formula (9), and a compound represented by formula (10).

[0217] As mentioned above, usually, the reactivity of the photo radical of the maleimide compound is very low. However, the bismaleimide compound (A) is as mentioned above, and the light transmittance is very excellent. In addition, the imidazole compound (B) is also excellent in light transmittance. Therefore, even if the resin composition contains the maleimide compound (D), by using the bismaleimide compound (A) together with the compound (B) and the compound (C) and the initiator (E) mixed as needed, even if various active energy rays are used, the light will fully reach the photocuring initiator, and the free radical reaction using the free radicals generated by the photocuring initiator will proceed, effectively causing the photo radical reaction of the maleimide, and can be photocured.

[0218] For the resin composition comprising maleimide compound (D), in the exposure process of making a multilayer printed circuit board, it also has excellent photocurability to various active energy rays, can be given excellent alkali developability in the developing process, and the obtained insulating layer has excellent adhesion to metals with adhesive properties such as titanium. In addition, the heat resistance, insulation reliability, and thermal stability of the obtained cured product are also excellent. Therefore, according to the present embodiment, it is possible to appropriately form a protective film and an insulating layer in a multilayer printed circuit board and a semiconductor device, and obtain a high-density printed circuit board and a semiconductor device with a high-precision pattern.

[0219] As the maleimide compound (D), from the viewpoint of being able to exhibit better curability, better heat resistance and thermal stability, better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, it is preferred that it contains at least one selected from the group consisting of the compound represented by formula (5), the compound represented by formula (6), and the compound represented by formula (7), and it is more preferred that it contains at least one selected from the group consisting of the compound represented by formula (5) and the compound represented by formula (6).

[0220] Next, the compounds represented by the formula (5) to (10) included in the maleimide compound (D) are described.

[0221] (Compound represented by formula (5))

[0222] The compound represented by formula (5) is the following compound.

[0223]

[0224] In formula (5), R 10 , R 11 , and R 12 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0225] As a linear or branched alkyl group having 1 to 8 carbon atoms which may optionally have a substituent, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, and a heptyl group can be cited. The hydrogen atoms in these alkyl groups may be substituted by halogen atoms such as fluorine atoms and chlorine atoms, and cyano groups. Among these alkyl groups, from the viewpoint of better photocurability, heat resistance, and thermal stability, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, preferably a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group, more preferably a methyl group, an ethyl group, and an isopropyl group, and further preferably a methyl group.

[0226] As the compound represented by formula (5), from the viewpoint of exhibiting better photocurability, heat resistance, and thermal stability, solubility in solvents, low melting point, low water absorption, and compatibility with other resins, the compound represented by formula (19) (also referred to as TMDM in this embodiment) is further more preferred.

[0227]

[0228] (Compound represented by formula (6))

[0229] The compound represented by formula (6) is the following compound.

[0230]

[0231] In formula (6), R 13 , R 14 , and R 15 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.

[0232] As the linear or branched alkyl group having 1 to 6 carbon atoms, reference may be made to R3 in the above formula (1). As the alkyl group, from the viewpoint of better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred, and a methyl group is more preferred.

[0233] In addition, for R 13 , R 14 , and R 15 From the viewpoint of showing better solubility in a solvent, R 13 and R 15 is a linear or branched alkyl group having 1 to 6 carbon atoms, and R 14 It should be noted that the preferred alkyl groups are as described above.

[0234] n2 is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, from the viewpoint of achieving better solubility in a solvent, obtaining a more appropriate viscosity, and being able to more appropriately control the increase in viscosity of the varnish.

[0235] As the compound represented by formula (6), commercially available products can be used, for example, the compound represented by formula (20) (BCPH01 (trade name, Mw / Mn=1.0-1.8) manufactured by Gunyoung Chemical Industry Co., Ltd., and BCPH13 (trade name, Mw / Mn=1.0-1.6) manufactured by Gunyoung Chemical Industry Co., Ltd.), and the compound represented by formula (21) (BMCX426 (trade name) manufactured by Gunyoung Chemical Industry Co., Ltd.).

[0236]

[0237] In formula (20), n 21 It is an integer from 1 to 5.

[0238]

[0239] In formula (21), n 22 It is an integer from 1 to 10.

[0240] (Compound represented by formula (7))

[0241] The compound represented by formula (7) is the following compound.

[0242]

[0243] In formula (7), R 16 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R 17 Each independently represents a hydrogen atom or a methyl group.

[0244] As R 16 From the viewpoint of better solubility in solvents, low melting point, low water absorption, and better compatibility with other resins, a methyl group or an ethyl group is preferred.

[0245] As R 17 From the viewpoint of exhibiting better solubility in a solvent, a low melting point, low water absorption, and better compatibility with other resins, a hydrogen atom is preferred.

[0246] As the maleimide compound represented by formula (7), a commercially available product can be used, and an example thereof is BMI-70 (trade name) manufactured by K.I. Chemical Industry Co., LTD. represented by formula (22).

[0247]

[0248] (Compound represented by formula (8))

[0249] The compound represented by formula (8) is the following compound.

[0250]

[0251] In formula (8), R 18 Each independently represents a hydrogen atom or a methyl group. n3 represents an integer of 1-10.

[0252] As the maleimide compound represented by formula (8), a commercially available product can be used, and examples thereof include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by formula (23).

[0253]

[0254] In formula (23), n 31 It is an integer from 1 to 10.

[0255] (Compound represented by formula (9))

[0256] The compound represented by formula (9) is the following compound.

[0257]

[0258] In formula (9), R 19 Each independently represents a hydrogen atom, a methyl group, or an ethyl group.

[0259] As R 19 From the viewpoint of exhibiting better solubility in a solvent, a low melting point, low water absorption, and better compatibility with other resins, a methyl group or an ethyl group is preferred.

[0260] As the maleimide compound represented by the formula (9), a commercially available product can be used, and an example thereof is BMI-80 (trade name) manufactured by K.I. Chemical Industry Co., LTD. represented by the formula (24).

[0261]

[0262] (Compound represented by formula (10))

[0263] The compound represented by formula (10) is the following compound.

[0264]

[0265] In formula (10), R 20 Each independently represents a hydrogen atom or a methyl group. n4 represents an integer of 1-10.

[0266] As R 20 From the viewpoint of exhibiting better solubility in a solvent, a low melting point, low water absorption, and better compatibility with other resins, a hydrogen atom is preferred.

[0267] As n4, an integer of 1 to 5 is more preferable from the viewpoints of obtaining a more appropriate viscosity and being able to more appropriately control the viscosity increase of the varnish, which leads to a better solubility in a solvent.

[0268] As the maleimide compound represented by the formula (10), a commercially available product can be used, and an example thereof is BMI-2300 (trade name) manufactured by Yamato Chemical Industry Co., Ltd. represented by the formula (25).

[0269]

[0270] In formula (25), n 41 It is an integer from 1 to 5.

[0271] In the resin composition, the total content of the maleimide compound (D) is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, further preferably 25 to 60 parts by mass, further more preferably 30 to 50 parts by mass, and further preferably 35 to 45 parts by mass based on 100 parts by mass of the resin solid content in the resin composition from the viewpoint of obtaining better heat resistance and thermal stability.

[0272] In addition, in the resin composition, the total content of the maleimide compound (D) is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, further preferably 25 to 60 parts by mass, further more preferably 30 to 50 parts by mass, and further preferably 35 to 45 parts by mass, relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (D), from the viewpoint of obtaining better heat resistance and thermal stability.

[0273] When the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) and also contains a compound (C), a compound (D), and an initiator (E), the content of the maleimide compound (D) is preferably 10 to 85 parts by mass, more preferably 15 to 80 parts by mass, further preferably 20 to 45 parts by mass, and further more preferably 25 to 40 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint of obtaining better heat resistance and thermal stability.

[0274] 〔Other maleimide compounds〕

[0275] The resin composition of the present embodiment may further include other maleimide compounds different from the bismaleimide compound (A) and the maleimide compound (D). Such other maleimide compounds are not particularly limited as long as they are compounds having one or more maleimide groups in the molecule. Examples of other maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidocaproic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl)-1,2 ...-ethyl)-1,2-diphenylmethanebismaleimide, bis(3- bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 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 Imidoethane, 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-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis( 3-maleimide phenoxy) benzene, 1,3-bis(4-maleimide phenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimide phenoxy) phenyl] propane, bis(3,5-dimethyl-4-citraconimide phenyl) methane, bis(3-ethyl-5-methyl-4-citraconimide phenyl) methane, bis(3,5-diethyl-4-citraconimide phenyl) methane, polyphenylmethane maleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds may be used alone or in combination of two or more.

[0276] As other maleimide compounds, compounds having excellent light transmittance are preferably used.

[0277] When other maleimide compounds are contained in the resin composition, the total content of other maleimide compounds is usually about 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0278] 〔Photocuring initiator (E)〕

[0279] The resin composition of this embodiment preferably further comprises a photocuring initiator (E). The photocuring initiator (E) is not particularly limited, and a known substance in the field of photocurable resin compositions can be used. The photocuring initiator (E) can be photocured using various active energy rays.

[0280] Examples of the photocuring initiator (E) 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, p-chlorobenzoyl peroxide, and di-tert-butyl diperphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl oxide; Phosphine, benzoyl-diphenyl-phosphine oxide, acylphosphine oxides such as bisbenzoyl-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholino)propane-1-one. phenyl)-butanone-1 and other acetophenones; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-dimethylaminobenzophenone and other benzophenones; 1-[4-( Radical photocuring initiators such as oxime esters such as 1-[(2-phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone 1-(O-acetyl oxime), a photocuring initiator represented by formula (26) (hereinafter, also referred to as “photocuring initiator (E1)”), and a photocuring initiator represented by formula (27) (hereinafter, also referred to as “photocuring initiator (E2)”),

[0281] Diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate; sulfonium salts of Lewis acids such as triphenylsulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate ester initiators; cationic photopolymerization initiators such as other photoacid generators.

[0282] As the photocuring initiator (E), 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) 784 (trade name) manufactured by IGM Resins BV, Irgacure (registered trademark) OXE01 (trade name) manufactured by BASF Japan Ltd., and Irgacure (registered trademark) OXE02 (trade name) manufactured by BASF Japan Ltd., etc.

[0283] These photocuring initiators (E) can be used alone or in combination of two or more.

[0284] For the photocuring initiator (E), a chloroform solution containing the photocuring initiator (E) at 0.01% by mass is prepared. When the absorbance of the chloroform solution containing the photocuring initiator (E) at 0.01% by mass is measured using active energy rays having a wavelength of 365nm (i-ray), the absorbance is preferably 0.1 or more, and the photocuring initiator (E) exhibits very excellent light absorption. In addition, when the absorbance of the chloroform solution containing the photocuring initiator (E) at 0.01% by mass is measured using active energy rays having a wavelength of 405nm (h-ray), the absorbance is preferably 0.1 or more, and in this case, very excellent light absorption is also exhibited. If such a photocuring initiator (E) is used, for example, when a printed circuit board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct drawing exposure method, a photoradical reaction of maleimide is effectively induced even when active energy rays having a wavelength of 405nm (h-ray) are used. It should be noted that, for the absorbance at a wavelength of 365nm (i-ray), from the aspect of being able to obtain a resin composition with better photocurability, it is more preferably 0.15 or more. For the absorbance at a wavelength of 405nm (h-ray), from the aspect of being able to obtain a resin composition with better photocurability, it is more preferably 0.15 or more. It should be noted that, for the absorbance at a wavelength of 365nm (i-ray) and the absorbance at a wavelength of 405nm (h-ray), the upper limit of each is, for example, 99.9 or less.

[0285] The content of the photocuring initiator (E) in the resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, further preferably 0.3 to 10 parts by mass, and further more preferably 1.0 to 9.0 parts by mass based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of not inhibiting the photocuring reaction in the resin composition, allowing the photocuring to proceed sufficiently, and making the exposed portion more sufficiently insolubilized in terms of alkali developability.

[0286] In addition, when the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) and also contains a compound (C), a compound (D), and an initiator (E), the content of the photocuring initiator (E) is preferably 0.1 to 20 parts by mass, more preferably 0.15 to 15 parts by mass, further preferably 0.2 to 10 parts by mass, and further preferably 1.0 to 9.0 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint of not inhibiting the photocuring reaction in the resin composition, allowing the photocuring to proceed more fully, and making the exposed portion more fully insolubilized in terms of alkali developability.

[0287] As the photocuring initiator (E), oxime esters and acylphosphine oxides are preferred because they have higher sensitivity to various active energy rays.

[0288] As oxime esters, from the perspective of higher sensitivity to various active energy rays and better solvent solubility, more preferred are 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone 1-(O-acetyl oxime), the photocuring initiator represented by formula (26), and the photocuring initiator represented by formula (27), and further preferred are the photocuring initiator represented by formula (26) and the photocuring initiator represented by formula (27).

[0289] The present inventors speculate that the resin composition has a higher sensitivity to various active energy rays and a better photocurability by including a photocuring initiator (E1) and / or a photocuring initiator (E2) while including a bismaleimide compound (A) and an imidazole compound (B) for the following reasons. That is, the photocuring initiator (E1) and the photocuring initiator (E2) have excellent compatibility with the bismaleimide compound (A) and the imidazole compound (B). Furthermore, these photocuring initiators have high absorbance to various active energy rays, especially active energy rays including i-rays with a wavelength of 365nm, and active energy rays including h-rays with a wavelength of 405nm, so active free radicals are easily generated. Therefore, it is speculated that in the exposure process, by irradiating various active energy rays, active free radicals are quickly generated by the photocuring initiator, and the free radicals quickly react with the bismaleimide compound (A), so that excellent photocurability is exhibited.

[0290] Therefore, the resin composition does not hinder the photocuring reaction in the exposure process of the multilayer printed circuit board, has excellent photocurability to various active energy rays, can be given excellent alkali developability in the development process, and the obtained insulating layer has excellent adhesion to adhesive metals such as titanium. In addition, the obtained cured product also has excellent heat resistance, insulation reliability, and thermal stability. Therefore, according to this embodiment, a protective film and an insulating layer in a multilayer printed circuit board and a semiconductor device can be appropriately formed to obtain a high-density printed circuit board and a semiconductor device with a high-precision pattern.

[0291] When the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) and also contains a compound (C), a compound (D), and an initiator (E), the total content of the photocuring initiator (E1) and the photocuring initiator (E2) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, further preferably 0.3 to 10 parts by mass, and further more preferably 0.5 to 8.0 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the viewpoint of being able to impart more excellent alkali developability, not inhibiting the photocuring initiator in the resin composition, and being able to exhibit good curing properties.

[0292] Next, the photocuring initiator (E1) and the photocuring initiator (E2) are described.

[0293] (Photocuring initiator (E1) represented by formula (26))

[0294] The photocuring initiator (E1) represented by the formula (26) is the following compound.

[0295]

[0296] In formula (26), R 25 represents an acetyl group or a benzoyl group. Among them, an acetyl group is preferred because it has a higher sensitivity to various active energy rays.

[0297] R 26 It represents a phenyl group or naphthyl group which may have a substituent. As such a group, for example, a phenyl group or naphthyl group having a substituent such as a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a tetrafluoropropoxy group, a pentafluoropropoxy group, a hexafluoropropoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxy group having 1 to 4 carbon atoms can be cited. Among them, tetrafluoropropoxyphenyl, pentafluoropropoxyphenyl, and hexafluoropropoxyphenyl are preferred, and tetrafluoropropoxyphenyl is more preferred because of their higher sensitivity to various active energy rays.

[0298] R 27represents a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent. Examples of the linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, a 5-ethylhexyl group, a 6-methylheptyl group, and an octyl group. Among them, 5-ethylhexyl group, 6-methylheptyl group, and an octyl group are preferred, and 5-ethylhexyl group is more preferred, because they exhibit better compatibility with the bismaleimide compound (A) and the imidazole compound (B).

[0299] R 28 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. As the linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, for example, R in formula (26) can be referred to. 27 Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred because they have better solvent solubility, and a methyl group is more preferred.

[0300] n5 each independently represents an integer of 1-5.

[0301] It should be noted that the photocuring initiator (E1) shown in formula (26) can be an initiator with a N-O bond in the (E) form, an initiator with a N-O bond in the (Z) form, or a mixture of an initiator with a N-O bond in the (E) form and an initiator with a N-O bond in the (Z) form.

[0302] As the photocuring initiator (E1) represented by formula (26), the photocuring initiator represented by formula (28) is further preferred because of its further higher sensitivity to various active energy rays, especially active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm, and its further excellent solvent solubility.

[0303]

[0304] It should be noted that the photocuring initiator represented by formula (28) can be an initiator with the N-O bond in the (E) form, an initiator with the N-O bond in the (Z) form, or a mixture of an initiator with the N-O bond in the (E) form and an initiator with the N-O bond in the (Z) form.

[0305] (Method for producing photocuring initiator (E1))

[0306] The photocuring initiator (E1) can be produced by a known method without particular limitation, and for example, the method described in JP-A-2014-500852 can be used.

[0307] The obtained photocuring initiator (E1) can be identified by known methods such as NMR (nuclear magnetic resonance analysis). The purity of the photocuring initiator (E1) can be analyzed, for example, by GPC, liquid chromatography, and IR spectroscopy. Volatile components such as by-products and residual solvents in the photocuring initiator (E1) can be quantitatively analyzed, for example, by GPC and gas chromatography. In the case where halogen atoms remain in the photocuring initiator (E1), the remaining halogen compounds can be identified, for example, using a liquid chromatography-mass spectrometer, or can be quantitatively determined by potentiometric titration using a silver nitrate solution or by ion chromatography after decomposition based on a combustion method.

[0308] (Photocuring initiator (E2) represented by formula (27))

[0309] The photocuring initiator (E2) represented by the formula (27) is the following compound.

[0310]

[0311] In formula (27), R 29 represents an aryl group having 6 to 24 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 24 carbon atoms which may have a substituent. Examples of the aryl group having 6 to 24 carbon atoms which may have a substituent include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a tetrafluoropropoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group. Examples of the heteroaryl group having 3 to 24 carbon atoms which may have a substituent include a pyrrolyl group, a furyl group, a benzofuranyl group, a thienyl group, a pyrazolyl group, an imidazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, a pyrimidinyl group, a pyrazinyl group, a quinolyl group, an isoquinolyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, a benzotriazolyl group, and a benzimidazolyl group. Among these, a benzofuranyl group and a benzothienyl group are preferred, and a benzofuranyl group is more preferred because of their higher sensitivity to various active energy rays.

[0312] R 30 represents an acetyl group or a benzoyl group. Among them, an acetyl group is preferred because it has a higher sensitivity to various active energy rays.

[0313] R 31represents a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent. Examples of the linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-ethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, an isopentyl group, a hexyl group, a 5-ethylhexyl group, and a heptyl group. Among them, isopentyl group, a hexyl group, and a 5-ethylhexyl group are preferred, and isopentyl group is more preferred because of the better compatibility with the bismaleimide compound (A) and the imidazole compound (B).

[0314] X represents an oxygen atom or a sulfur atom. Among them, a sulfur atom is preferred because of its higher sensitivity to various active energy rays.

[0315] It should be noted that the photocuring initiator (E2) shown in formula (27) can be an initiator with the N-O bond in the (E) form, an initiator with the N-O bond in the (Z) form, or a mixture of an initiator with the N-O bond in the (E) form and an initiator with the N-O bond in the (Z) form.

[0316] As the photocuring initiator (E2) represented by formula (27), the photocuring initiator represented by formula (29) is further preferred because of its higher sensitivity to various active energy rays, especially active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm, and its better solvent solubility.

[0317]

[0318] It should be noted that the photocuring initiator represented by formula (29) can be an initiator with the N-O bond in the (E) form, an initiator with the N-O bond in the (Z) form, or a mixture of an initiator with the N-O bond in the (E) form and an initiator with the N-O bond in the (Z) form.

[0319] (Method for producing photocuring initiator (E2))

[0320] The photocuring initiator (E2) can be produced by a known method without particular limitation, and for example, the method described in JP-A-2016-531926 can be used.

[0321] The obtained photocuring initiator (E2) can be identified by known methods such as NMR (nuclear magnetic resonance analysis). The purity of the photocuring initiator (E2) can be analyzed, for example, by GPC, liquid chromatography, and IR spectroscopy. Volatile components such as byproducts and residual solvents in the photocuring initiator (E2) can be quantitatively analyzed, for example, by GPC and gas chromatography. In the case where halogen atoms remain in the photocuring initiator (E2), the remaining halogen compounds can be identified, for example, using a liquid chromatography-mass spectrometer, or can be quantitatively determined by potentiometric titration using a silver nitrate solution or by ion chromatography after decomposition based on a combustion method.

[0322] In the present embodiment, from the perspective of having better photocurability to various active energy rays, especially active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm, and that a high-density printed circuit board and a semiconductor device with a high-precision pattern can be obtained by using the resin composition, it is preferred that the photocuring initiator (E1) and / or the photocuring initiator (E2) also contain an acylphosphine oxide.

[0323] The present inventors speculated on the reasons as follows. That is, the photocuring initiator (E1) and the photocuring initiator (E2) have a high absorbance to various active energy rays (light), especially active energy rays of i-rays with a wavelength of 365nm, and active energy rays of h-rays with a wavelength of 405nm. Moreover, for the photocuring initiator (E1) and the photocuring initiator (E2), the free radical generation density is not easily lost even on the surface in contact with air, so the surface curability is also very excellent. Due to its structure, the acylphosphine oxide class has a high absorbance to various active energy rays (light), especially active energy rays of i-rays with a wavelength of 365nm, and active energy rays of h-rays with a wavelength of 405nm. By using it together with the photocuring initiator (E1) and / or the photocuring initiator (E2), it can have a more excellent photocurability. Moreover, the transmittance of the bismaleimide compound (A) and the imidazole compound (B) to various active energy rays is also excellent. Based on the above, by using these, the resin composition can be cured relatively uniformly from the surface in contact with air to the inside (deep part) not in contact with air.

[0324] When the resin composition contains a bismaleimide compound (A) and an imidazole compound (B), contains a photocuring initiator (E1) and / or a photocuring initiator (E2), contains an acylphosphine oxide, and also contains the compound (C) and the compound (D), the total content of the photocuring initiator (E1) and the photocuring initiator (E2) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), the photocuring initiator (E1), the photocuring initiator (E2), and the acylphosphine oxide, from the viewpoint of being able to impart more excellent alkali developability, not inhibiting the photocuring initiator in the resin composition, and being able to exhibit good curing properties. The total content of the acylphosphine oxides is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the total of the bismaleimide compound (A), the imidazole compound (B), the compound (C), the compound (D), the photocuring initiator (E1), the photocuring initiator (E2), and the acylphosphine oxides.

[0325] When the resin composition contains a bismaleimide compound (A) and an imidazole compound (B) and also contains a compound (C), a compound (D), and an initiator (E), the total content of the acylphosphine oxides is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, further preferably 0.3 to 10 parts by mass, and further more preferably 0.5 to 5.0 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), from the perspective of being able to impart more excellent alkali developability, not inhibiting the photocuring initiator in the resin composition, and being able to exhibit good curing properties.

[0326] As the acylphosphine oxide, the compound represented by formula (30) is preferred. The compound represented by formula (30) has a higher absorbance to various active energy rays (light rays), especially active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm. In addition, by using it together with the photocuring initiator (E1) and / or the photocuring initiator (E2), it is also possible to have a more excellent photocurability.

[0327]

[0328] In formula (30), R 32 Each independently represents a substituent represented by formula (31) or a phenyl group. 32In the above, preferably, one or more substituents are represented by the formula (31).

[0329]

[0330] In formula (31), R 33 Each independently represents a hydrogen atom or a methyl group. In formula (31), -* represents and R in formula (30) 32 Atomic bonds directly connected to phosphorus atoms (P). 33 Among them, preferably at least one is a methyl group, and more preferably all are methyl groups.

[0331] For the compound represented by formula (30), a chloroform solution containing the compound at 0.01% by mass is prepared, and when the absorbance of the chloroform solution is measured using active energy rays containing a wavelength of 365nm (i-ray), if the absorbance is 0.1 or more, the light having a wavelength of 365nm (i-ray) exhibits very excellent absorptivity. Therefore, the compound appropriately generates free radicals for light having a wavelength of 365nm (i-ray). The absorbance is preferably 0.15 or more. The upper limit is, for example, 99.9 or less.

[0332] For the compound represented by formula (30), a chloroform solution containing the compound at 0.01% by mass is prepared, and when the absorbance of the chloroform solution is measured using an active energy ray containing a wavelength of 405nm (h-ray), when the absorbance is 0.1 or more, the light of the wavelength of 405nm (h-ray) exhibits very excellent absorbance. If such a photocuring initiator is used, for example, when a printed circuit board having a high density and high-precision wiring formation (pattern) is manufactured using a direct drawing exposure method, even when an active energy ray containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is effectively caused. The absorbance of the wavelength of 405nm (h-ray) is more preferably 0.15 or more from the aspect of being able to obtain a resin composition with better photocurability. The upper limit value is, for example, 99.9 or less.

[0333] As the compound represented by formula (30), for example, acyl phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide can be cited. Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred from the aspects of better compatibility with bismaleimide compound (A) and imidazole compound (B), better solvent solubility, better light transmittance, and better photocurability when used together with curing initiator (E1) and / or photocuring initiator (E2). These compounds can be used alone or in combination of two or more.

[0334] 〔Filling material〕

[0335] The resin composition of the present embodiment may contain a filler in order to improve properties such as coating properties and heat resistance. The filler is preferably a filler that has insulating properties and does not inhibit the permeability of various active energy rays used in photocuring.

[0336] As fillers, for example, silica (e.g., natural silica, fused silica, amorphous silica, and hollow silica), aluminum compounds (e.g., boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride), boron compounds (e.g., boron nitride), magnesium compounds (e.g., magnesium oxide, and magnesium hydroxide), calcium compounds (e.g., calcium carbonate), molybdenum compounds (e.g., molybdenum oxide, and zinc molybdate), barium compounds (e.g., barium sulfate, and barium silicate), talc (e.g., natural talc, and calcined talc), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass, E glass, T glass, and D glass), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth) acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers can be used alone or in combination of two or more.

[0337] Among these, at least one selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber is preferred.

[0338] These fillers may be surface-treated with a silane coupling agent or the like described below.

[0339] From the viewpoint of further improving the heat resistance of the cured product and obtaining better coating properties, silicon dioxide is preferred, and fused silica is more preferred. Specific examples of silicon dioxide include SFP-130MC (trade name) manufactured by Denka Corporation, SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by ADMATECHS CO., LTD.

[0340] The particle size of the filler is not particularly limited, but is usually 0.005 to 10 μm, preferably 0.01 to 1.0 μm, from the viewpoint of further improving the ultraviolet light transmittance of the resin composition.

[0341] In the resin composition, for the content of the filler, from the viewpoint of making the light transmittance of the resin composition and the heat resistance of the cured product better, it is usually preferably set to 300 mass parts or less, more preferably set to 200 mass parts or less, and further preferably set to 100 mass parts or less relative to 100 mass parts of the resin solid component in the resin composition. It should be noted that, in the case of containing the filler, for the lower limit, from the viewpoint of obtaining the effect of further improving the coating film property, heat resistance and other characteristics, it is usually 1 mass part relative to 100 mass parts of the resin solid component in the resin composition.

[0342] 〔Silane coupling agent and wetting and dispersing agent〕

[0343] In order to further improve the dispersibility of the filler and the bonding strength between the polymer and / or resin and the filler, a silane coupling agent and / or a wetting and dispersing agent may be used in combination in the resin composition of the present embodiment.

[0344] As these silane coupling agents, there is no particular limitation as long as they are silane coupling agents used for surface treatment of inorganic substances. For example, 3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, 3-aminopropyl dimethoxymethyl silane, 3-aminopropyl diethoxymethyl silane, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl dimethoxymethyl silane, N-(2-aminoethyl)-3-aminopropyl diethoxymethyl silane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, [3-(6-aminohexylamino)propyl] trimethoxysilane, and [3-(N,N- Aminosilanes such as [2,4-dimethylamino]-propyl]trimethoxysilane; γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, and trimethoxy(4- Vinyl silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, etc. methacryl silanes; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, etc. acryl silanes; 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, etc. isocyanate silanes; tris-(trimethoxysilylpropyl)isocyanurate, etc. isocyanurate silanes; 3-mercaptopropyltrimethoxysilane, 3- Mercaptosilanes such as mercaptopropyl dimethoxymethylsilane; ureidosilanes such as 3-ureidopropyl triethoxysilane; styrylsilanes such as p-styryl trimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl-γ-aminopropyl trimethoxysilane hydrochloride; anhydride systems such as [3-(trimethoxysilyl)propyl] succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; arylsilanes such as trimethoxy (1-naphthyl) silane. These silane coupling agents can be used alone or in combination of two or more.

[0345] In the resin composition, the content of the silane coupling agent is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0346] As a wetting and dispersing agent, there is no particular limitation as long as it is a dispersion stabilizer used for coatings. As a specific example, for example, 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 Japan KK can be cited. These wetting and dispersing agents can be used alone or in combination of two or more.

[0347] In the resin composition, the content of the wetting and dispersing agent is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0348] [Cyanate compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds]

[0349] In the present embodiment, as long as the effects of the present invention are exerted, various compounds and resins such as bismaleimide compound (A), imidazole compound (B), compound (C), maleimide compound (D), other maleimide compounds, and photocuring initiator (E) can be used according to the flame retardancy, heat resistance, and thermal expansion characteristics of the cured product. In addition, these compounds and resins are preferably such that when exposed to various active energy rays, especially active energy rays including i-rays with a wavelength of 365nm and active energy rays including h-rays with a wavelength of 405nm, the resin composition is photosensitive and photocured.

[0350] These compounds and resins may be used alone or in combination of two or more.

[0351] <Cyanate Compounds>

[0352] The cyanate compound is not particularly limited as long as it is a resin having an aromatic portion substituted with at least one cyanato group in the molecule.

[0353] For example, there can be mentioned a compound represented by formula (32).

[0354]

[0355] In formula (32), Ar1 represents a benzene ring, a naphthalene ring, or two benzene rings bonded together by a single bond. When there are multiple groups, they may be the same or different. Ra each 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 alkoxy group having 1 to 4 carbon atoms, and a group formed by bonding an alkyl group having 1 to 6 carbon atoms to an aryl group having 6 to 12 carbon atoms. The aromatic ring in Ra may have a substituent, and the substituents in Ar1 and Ra may be selected at any position. p represents the number of cyano groups bonded to Ar1, and is independently 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 it is two benzene rings bonded together by a single bond. t represents the average number of repetitions, which is an integer of 0 to 50, and the cyanate compound may be a mixture of compounds having different t. When there are multiple Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted with a heteroatom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN-, wherein R represents an organic group), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyldioxy group (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom, or a divalent oxygen atom.

[0356] The alkyl group in Ra of the formula (32) may have any structure of a linear or branched structure, or a cyclic structure (eg, a cycloalkyl group).

[0357] Furthermore, the hydrogen atoms in the alkyl group in the formula (32) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group.

[0358] Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl.

[0359] Specific examples of the alkenyl group include vinyl, (meth)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl, 2-pentenyl, and 2-hexenyl.

[0360] Specific examples of the aryl group include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, and o-, m- or p-tolyl.

[0361] Examples of the alkoxy 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.

[0362] Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of formula (32) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, and phthalide diyl. The hydrogen atoms in the divalent organic group may be substituted by halogen atoms such as fluorine atoms and chlorine atoms, alkoxy groups such as methoxy and phenoxy, and cyano groups.

[0363] Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the formula (32) include an imino group and a polyimide group.

[0364] In addition, examples of the organic group represented by X in formula (32) include an organic group having a structure represented by formula (33) or an organic group having a structure represented by formula (34).

[0365]

[0366] In formula (33), Ar2 represents a benzene diyl group, a naphthalene diyl group, or a biphenyl diyl group, and when u is an integer greater than 2, they are optionally the same or different from each other. 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 represent any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer from 0 to 5.

[0367]

[0368] In formula (34), Ar3 represents a benzene diyl group, a naphthalene diyl group, or a biphenyl diyl group, and when v is an integer greater than 2, they are optionally the same or different from each other. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least one cyano group. v represents an integer from 0 to 5, and may be a mixture of compounds having different v.

[0369] Furthermore, as X in the formula (32), there can be mentioned a divalent group represented by the following formula.

[0370]

[0371] In the formula herein, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0372] Specific examples of Ar2 of formula (33) and Ar3 of formula (34) include a benzene diyl group in which two carbon atoms shown in formula (33) or two oxygen atoms shown in formula (34) are bonded to the 1,4 position or the 1,3 position, a biphenyl diyl group in which two carbon atoms or two oxygen atoms are bonded to the 4,4' position, 2,4' position, 2,2' position, 2,3' position, 3,3' position or 3,4' position, and a naphthalene diyl group in which two carbon atoms or two oxygen atoms are bonded to the 2,6 position, 1,5 position, 1,6 position, 1,8 position, 1,3 position, 1,4 position or 2,7 position.

[0373] The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf, and Rg in formula (33) and Ri and Rj in formula (34) have the same meanings as in formula (32).

[0374] Specific examples of the cyano-substituted aromatic compound represented by formula (32) include cyanobenzene, 1-cyano-2-methylbenzene, 1-cyano-3-methylbenzene, or 1-cyano-4-methylbenzene, 1-cyano-2-methoxybenzene, 1-cyano-3-methoxybenzene, or 1-cyano-4-methoxybenzene, 1-cyano-2,3-dimethylbenzene, 1-cyano-2,4-dimethylbenzene, 1-cyano-2,5-dimethylbenzene, 1-cyano-2,6-dimethylbenzene, 1-cyano-3,4-dimethylbenzene, or 1-cyano-3,5-dimethylbenzene, cyanoethylbenzene, cyanobutylbenzene, cyanooctylbenzene, cyanononylbenzene, 2-(4-cyanophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyano-4-cyclohexylbenzene, 1-cyano-4-vinylbenzene, 1-cyano-2-chlorobenzene or 1-cyano-3-chlorobenzene, 1-cyano-2,6-dichlorobenzene, 1-cyano-2-methyl-3-chlorobenzene, cyanonitrobenzene, 1-cyano-4-nitro-2-ethylbenzene, 1-cyano-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanophenyl) sulfide, 1-cyano-3-trifluoromethylbenzene, 4-cyanobiphenyl, 1-cyano-2-acetylbenzene or 1-cyano-4-acetylbenzene, 4-cyanobenzaldehyde, 4-cyanobenzoic acid methyl ester, 4-cyanobenzoic acid phenyl ester, 1-cyano-4-ethyl acylaminobenzene, 4-cyanobenzophenone, 1-cyano-2,6-di-tert-butylbenzene, 1,2-dicyanobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,4-dicyano-2-tert-butylbenzene, 1,4-dicyano-2,4-dimethylbenzene, 1,4-dicyano-2,3,4-dimethylbenzene, 1,3-dicyano-2,4,6-trimethylbenzene, 1,3-dicyano-5-methylbenzene, 1-cyano or 2-cyanonaphthalene, 1-cyano-4-methoxynaphthalene, 2-cyano-6-methoxynaphthalene, 2-cyano-7-methoxynaphthalene, 2,2'-dicyano-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3 2,6- or 2,7-dicyanonaphthalene, 2,2'- or 4,4'-dicyanobiphenyl, 4,4'-dicyanooctafluorobiphenyl, 2,4'- or 4,4'-dicyanodiphenylmethane, bis(4-cyano-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanophenyl)ethane, 1,1-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl)propane, 2,2-bis(4-cyano-3-methylphenyl)propane, 2,2-bis(2-cyano-5-biphenyl)propane, 2,2-bis(4-cyanophenyl)hexafluoropropane, 2,2-bis(4-cyano-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanophenyl)butane, 1,1-bis(4-cyanophenyl)isobutane, 1,1-bis(4-cyanophenyl)pentane, 1,1-bis(4-cyanophenyl)-3-methylbutane, 1,1-bis(4-cyanophenyl)-2-methylbutane, 1,1-bis(4-cyanophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanophenyl)butane, 2,2-bis(4-cyanophenyl)pentane, 2,2-bis(4-cyanophenyl)hexane, 2,2-bis(4-cyanophenyl)-3-methylbutane, 2,2-bis(4-cyanophenyl)-4-methylpentane, 2,2-bis(4-cyanophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanophenyl)hexane, 3,3 -bis(4-cyanophenyl)heptane, 3,3-bis(4-cyanophenyl)octane, 3,3-bis(4-cyanophenyl)-2-methylpentane, 3,3-bis(4-cyanophenyl)-2-methylhexane, 3,3-bis(4-cyanophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanophenyl)-3-methylheptane, 3,3-bis(4-cyanophenyl)-2-methylheptane, 3,3-bis(4-cyanophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanophenyl)-1,1,1,3 ,3,3-hexafluoropropane, bis(4-cyanophenyl)phenylmethane, 1,1-bis(4-cyanophenyl)-1-phenylethane, bis(4-cyanophenyl)biphenylmethane, 1,1-bis(4-cyanophenyl)cyclopentane, 1,1-bis(4-cyanophenyl)cyclohexane, 2,2-bis(4-cyano-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanophenyl)cyclohexane, bis(4-cyanophenyl)diphenylmethane, bis(4-cyanophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,1-bis(4-cyanophenyl) 1,3-Bis(4-cyanophenyl)-2-propene-1-one, bis(4-cyanophenyl) ether, bis(4-cyanophenyl) sulfide, bis(4-cyanophenyl) sulfone, 4-cyanobenzoic acid-4-cyanophenyl ester (4-cyanophenyl-4-cyanobenzoate), bis-(4-cyanophenyl) carbonate, 1,3-bis(4-cyanophenyl)adamantane, 1,3-bis(4-cyanophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-Bis(4-cyano-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanophenyl)fluorene, 9,9-bis(4-cyano-3-methylphenyl)fluorene, 9,9-bis(2-cyano-5-biphenyl)fluorene, tris(4-cyanophenyl)methane, 1,1,1-tris(4-cyanophenyl)ethane, 1,1,3-tris(4-cyanophenyl) 1,3,5-triazine, 2,4-bis(N-methyl-4-cyanophenyl)-6-(N-methylanilino)-1,3,5-triazine, bis(N-methyl-4-cyanophenyl)-6-(N-methylanilino)-1,3,5-triazine, 1,1,2,2-tetrakis(4-cyanophenyl)ethane, 1,3,5-tetrakis(4-cyanophenyl)methane, 1,1,2,2-tetrakis(4-cyanophenyl)ethane, 1,3,5-tetrakis(4-cyanophenyl)methane, 2,4,6-tris(N-methyl-4-cyanophenyl)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanophenyl)-6-(N-methylanilino)-1,3,5-triazine, 1,1,2,2-tetrakis(4-cyanophenyl)ethane, 1,3,5-tetrakis(4-cyanophenyl)methane ...3,5-tetrakis(4-cyanophenyl) -4-cyano-2-methylphenyl)-4,4'-oxybisphthalimide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxybisphthalimide, bis(N-4-cyanophenyl)-4,4'-oxybisphthalimide, bis(N-4-cyano-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanobenzyl) phenyl) isocyanurate, 2-phenyl-3,3-bis(4-cyanophenyl)benzodicarboxamidine, 2-(4-methylphenyl)-3,3-bis(4-cyanophenyl)benzodicarboxamidine, 2-phenyl-3,3-bis(4-cyanophenyl-3-methylphenyl)benzodicarboxamidine, 1-methyl-3,3-bis(4-cyanophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanophenyl)indolin-2-one.

[0375] These cyanate compounds may be used alone or in combination of two or more.

[0376] As another specific example of the cyanate compound represented by formula (32), there can be mentioned phenol novolac resin and cresol novolac resin (obtained 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 novolac resin (obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene novolac resin (obtained by reacting a fluorenone compound with 9,9-bis(hydroxyaryl)fluorene) Aralkyl resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, and biphenyl aralkyl resins (obtained by reacting a dihalogenated methyl compound such as Ar4-(CH2Y)2 (Ar4 represents a phenyl group, and Y represents a halogen atom. The same shall apply to this paragraph hereinafter) with a phenol compound in the presence of an acidic catalyst or in the absence of a catalyst, and a dihalogenated methyl compound such as Ar4-(CH2OR)2 (R represents an alkyl group) with a phenol compound in the presence of an acidic catalyst or in the absence of a catalyst. The present invention also includes phenolic resins obtained by reacting a (hydroxymethyl) compound with a phenol compound in the presence of an acidic catalyst, or a bis(hydroxymethyl) compound such as Ar4-(CH2OH)2 with a phenol compound in the presence of an acidic catalyst, or a phenolic resin obtained by polycondensing an aromatic aldehyde compound, an aralkyl compound and a phenol compound), phenol-modified xylene formaldehyde resin (obtained by reacting a xylene formaldehyde resin with a phenol compound in the presence of an acidic catalyst by a known method), a modified naphthalene formaldehyde resin (obtained by reacting a naphthalene formaldehyde resin with a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), a phenol-modified dicyclopentadiene resin, or a phenolic resin having a polynaphthylene ether structure (obtained by dehydrating and condensing a polyhydroxy naphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of an alkaline catalyst by a known method), and prepolymers thereof. These cyanate compounds may be used alone or in combination of two or more.

[0377] There is no particular limitation on the method for producing these cyanate ester compounds, and known methods can be used. As a specific example, a method of obtaining or synthesizing a hydroxyl-containing compound having a desired skeleton and modifying the hydroxyl group by a known method to perform cyanate esterification can be cited. As a method for cyanate esterification of a hydroxyl group, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional can be cited.

[0378] Cured products using these cyanate compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

[0379] In the resin composition, the content of the cyanate ester compound is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0380] <Phenolic resin>

[0381] As the phenol resin, any generally known phenol resin may 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, phenolic resin containing polymerizable unsaturated hydrocarbon group, and hydroxyl-containing silicone resins, etc. These phenolic resins can be used alone or in combination of two or more.

[0382] In the resin composition, the content of the phenolic resin is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0383] <Oxetane resin>

[0384] As oxetane resin, generally known substances can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (Toa Synthetics Co., Ltd., trade name), OXT-121 (Toa Synthetics Co., Ltd., trade name) and OXT-221 (Toa Synthetics Co., Ltd., trade name) etc. can be mentioned. These oxetane resins can be used alone or can be used in a suitable mixture of two or more.

[0385] In the resin composition, the content of the oxetane resin is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0386] <Benzoxazine compounds>

[0387] As a benzoxazine compound, as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, a generally known compound can be used. For example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), Pd type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), Fa type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), and phenolphthalein type benzoxazine, etc. can be cited. These benzoxazine compounds can be used alone or in combination of two or more.

[0388] In the resin composition, the content of the benzoxazine compound is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0389] <Epoxy resin>

[0390] The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylene novolac epoxy resin, multifunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolac epoxy resin, naphthylene ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, quadrifunctional phenol epoxy resin, triglycidyl isocyanurate Acid esters, glycidyl ester epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac epoxy resins, biphenyl novolac epoxy resins, phenol aralkyl novolac epoxy resins, naphthol aralkyl novolac epoxy resins, aralkyl novolac epoxy resins, naphthol aralkyl novolac epoxy resins, dicyclopentadiene epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds obtained by epoxidizing double bonds of butadiene, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins may be used alone or in combination of two or more.

[0391] As the epoxy resin, commercially available products can be used, for example, the epoxy resin represented by formula (35) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., in formula (35), n5 is about 4) and the naphthalene-type epoxy resin represented by formula (36) (HP-4710 (trade name) manufactured by DIC Corporation).

[0392]

[0393] These epoxy resins may be used alone or in combination of two or more.

[0394] In the resin composition, the content of the epoxy resin is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0395] <Other compounds>

[0396] As other compounds, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methyl styrene, ethyl styrene, and divinylbenzene; triallyl isocyanurate, trimethallyl isocyanurate, and bisallyl nadic-imide, etc. These compounds may be used alone or in combination of two or more.

[0397] In the resin composition, the content of other compounds is 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0398] 〔Organic solvent〕

[0399] In the resin composition of the present embodiment, an organic solvent may be contained as required. If an organic solvent is used, the viscosity during the preparation of the resin composition can be adjusted. For the type of organic solvent, as long as a part or all of the resin in the resin composition can be dissolved, there is no particular limitation. Examples of the organic solvent include halogen-containing solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene, etc.

[0400] Among these, from the viewpoint of showing better solubility in the bismaleimide compound (A) and the imidazole compound (B), and the compound (C), the compound (D), and the photocuring initiator (E) mixed as needed, and other resins and compounds, aprotic polar solvents, ketone solvents, cellosolve solvents, and ester solvents are preferred, and from the viewpoint of showing better solubility, aprotic polar solvents, ketone solvents, and ester solvents are more preferred.

[0401] As the aprotic polar solvent, dimethylacetamide is preferred. As the ketone solvent, methyl ethyl ketone is preferred. As the cellosolve solvent, propylene glycol monomethyl ether is preferred. As the ester solvent, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred.

[0402] These organic solvents may be used alone or in combination of two or more.

[0403] [Other ingredients]

[0404] The resin composition of the present embodiment may also be used in combination with various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, and elastomers, which have not been listed so far, within the range that does not impair the characteristics of the present embodiment; flame retardant compounds that have not been listed so far; additives, etc. These are not particularly limited as long as they are commonly used substances. For example, flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine; oxazine ring-containing compounds; phosphorus compounds such as phosphorus compounds such as phosphate esters, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. As additives, ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface adjusters, glossing agents, inhibitors, and thermosetting accelerators, etc. These components can be used alone or in combination of two or more.

[0405] In the resin composition, the content of other components is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0406] [Resin composition and method for producing varnish]

[0407] The resin composition of the present embodiment can be prepared by appropriately mixing the bismaleimide compound (A) and the imidazole compound (B), and the compound (C) as required, the maleimide compound (D), other maleimide compounds, a photocuring initiator (E), a filler, and other resins, other compounds, and additives. The method for preparing the resin composition can include, for example, a method in which the aforementioned components are sequentially mixed in a solvent and fully stirred.

[0408] When manufacturing resin combination, as required, known processing (stirring, mixing, and mixing treatment, etc.) for making each component uniformly dissolve or disperse can be carried out. Specifically, by using a stirring tank equipped with a stirrer with suitable stirring ability to carry out stirring and dispersing treatment, the dispersibility of each component such as bismaleimide compound (A) and imidazole compound (B) in resin combination can be improved. Stirring, mixing, and mixing treatment can be suitably carried out using known devices such as stirring devices for the purpose of dispersion, three-roll mill, ball mill, bead mill, and sand mill, etc., or mixing devices for the purpose of revolution or autogenous type, etc., for example. In addition, during the preparation of resin combination, organic solvent can be used as required. For the type of organic solvent, as long as the resin in the resin combination can be dissolved, it is not particularly limited, and its specific example is as mentioned above.

[0409] The resin composition can be used appropriately as a varnish when making 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 other than the organic solvent in the resin composition, and performing the aforementioned known treatment (stirring, mixing, and kneading treatment, etc.). It should be noted that the organic solvent used in the preparation of the varnish is not particularly limited, and its specific example is as described above.

[0410] [use]

[0411] The resin combination of the present embodiment can be suitable for the making of multilayer printed circuit boards, and preferably can be used for the purposes of the resin combination needing insulation.For example, it can be used for photosensitive film, photosensitive film with support, prepreg, resin sheet, circuit substrate (laminate purposes, multilayer printed circuit board purposes etc.), solder resist, bottom filling material, chip bonding material, semiconductor sealing material, hole-filling resin and component embedding resin etc. Among these, the photocurability and alkali developing property of resin combination are excellent, therefore, can be suitable for the solder resist of multilayer printed circuit board.In addition, the photocurability and alkali developing property of resin combination are excellent, and the metal of adhesiveness such as titanium has excellent adhesion, therefore, can be suitably used as the insulating layer of multilayer printed circuit board.

[0412] [cured material]

[0413] The cured product is obtained by curing the resin composition. The cured product can be obtained by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light. For the wavelength region of light, it is preferred to cure in the range of 100 to 500 nm where curing is effectively performed using a photopolymerization initiator or the like.

[0414] [Resin sheet]

[0415] The resin sheet of the present embodiment is a resin sheet with a support having 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 manufactured by coating the resin composition on the support and drying it. The resin layer in the resin sheet has excellent photocurability and alkali developability. In addition, the insulating layer obtained using the resin sheet has excellent adhesion to adhesive metals such as titanium.

[0416] The support may be a known object, without particular limitation, and is preferably a resin film. As the resin film, for example, 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 can be cited. Among these, PET film is preferred.

[0417] For the resin film, in order to facilitate the peeling from the resin layer, it is preferred to apply a peeling agent on the surface. The thickness of the resin film is preferably in the range of 5 to 100 μm, more preferably in the range of 10 to 50 μm. When the thickness is less than 5 μm, there is a tendency that the support is easily broken when the support is peeled off before alkali development, and when the thickness exceeds 100 μm, there is a tendency that the resolution is reduced when the support is exposed. In this specification, the thickness can be measured using a micrometer, for example.

[0418] Furthermore, in order to reduce scattering of light during exposure, the resin film preferably has excellent transparency.

[0419] Furthermore, in the resin sheet, the resin layer may be protected by a protective film.

[0420] By protecting the resin layer side with a protective film, it is possible to prevent dust and the like on the surface of the resin layer from being attached or damaged. 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. When the thickness is less than 1 μm, the handling properties of the protective film tend to be reduced, and if it exceeds 50 μm, it tends to be less cheap. It should be noted that the protective film is preferably such that the bonding force between the resin layer and the protective film is smaller than the bonding force between the resin layer and the support.

[0421] Examples of the method for producing a resin sheet include a method of applying a resin composition to a support such as a PET film and drying the composition to remove an organic solvent.

[0422] The coating method can be carried out by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a knife coater, or an extrusion coater. Drying can be carried out, for example, by heating in a dryer at 60 to 200° C. for 1 to 60 minutes.

[0423] The amount of organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer in order to further prevent diffusion of the organic solvent in subsequent steps. The thickness of the resin layer is preferably 1 to 50 μm in order to improve handling properties.

[0424] From the viewpoint of better handling properties, the resin sheet can be preferably used for production of an insulating layer of a multilayer printed wiring board.

[0425] [Multilayer printed circuit board]

[0426] The multilayer printed circuit 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. For the insulating layer, for example, more than one resin sheet can be overlapped and cured to obtain it. The number of stacking layers of the insulating layer and the conductor layer can be appropriately set according to the target use. In addition, the order of the insulating layer and the conductor layer is not particularly limited. As the conductor layer, it can be a metal foil used in various printed circuit board materials, for example, metal foils such as copper and aluminum can be mentioned. As the copper metal foil, copper foils such as rolled copper foil and electrolytic copper foil can be mentioned. The thickness of the conductor layer is generally 1 to 100 μm. Specifically, it can be manufactured by the following method.

[0427] (Lamination process)

[0428] In the lamination process, a vacuum laminator is used to laminate the resin layer side of the resin sheet on one or both sides of the circuit substrate. As the circuit substrate, for example, a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate can be cited. It should be noted that the circuit substrate refers to a substrate having a patterned conductor layer (circuit) formed on one or both sides of the substrate as described above. In addition, in a multilayer printed circuit board formed by alternately stacking a conductor layer and an insulating layer, a substrate having a patterned conductor layer (circuit) formed on one or both sides of the outermost layer of the multilayer printed circuit board is also included in the circuit substrate. It should be noted that the insulating layer stacked on the multilayer printed circuit board can be an insulating layer obtained by overlapping and curing more than one resin sheet of the present embodiment, or it can be an insulating layer obtained by overlapping more than one resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. It should be noted that the overlapping method of 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 conductor layer surface can be pre-roughened by blackening and / or copper etching. In the lamination process, when the resin sheet has a protective film, after the protective film is peeled off and removed, the resin sheet and the circuit substrate are preheated as required, and the resin layer of the resin sheet is pressed onto the circuit substrate while pressurizing and heating. In the present embodiment, it is suitable to use a method in which the resin layer of the resin sheet is laminated to the circuit substrate under reduced pressure by a vacuum lamination method.

[0429] The conditions of the lamination process are preferably, 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 , the pressing time is set to 5 to 300 seconds, and the air pressure is set to 20 mmHg or less under reduced pressure for lamination. In addition, the lamination process can be intermittent or continuous using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage lamination laminator made by Nikko-Materials Co., Ltd. can be cited.

[0430] (Exposure process)

[0431] 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 various active energy rays as a light source to cure the irradiated portion of the resin layer. The compound (C) added as needed does not inhibit the photocuring reaction in the exposure step.

[0432] Irradiation may be performed through a mask pattern or by direct irradiation. Examples of active energy rays include ultraviolet rays, visible 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 irradiation amount is approximately 5 to 1000 mJ / cm 2 In addition, when a printed circuit board having high density and high-precision wiring formation (pattern) is manufactured using a stepper that performs projection exposure by a step and repeat method, as active energy rays, for example, active energy rays containing a wavelength of 365nm (i-ray) are used. When active energy rays containing a wavelength of 365nm (i-ray) are used, the irradiation amount is approximately 5 to 10,000mJ / cm 2 When a printed circuit board having high density and high-precision wiring formation (pattern) is manufactured by direct drawing exposure method, it is preferable to use active energy rays including a wavelength of 405nm (h-ray) as active energy rays. When active energy rays including a wavelength of 405nm (h-ray) are used, the irradiation amount is approximately 10 to 10,000mJ / cm 2 .

[0433] The exposure method using the mask pattern includes a contact exposure method in which the mask pattern is closely attached to the multilayer printed circuit board, and a non-contact exposure method in which the exposure is performed using a lens or a mirror in a non-closed state. Any method can be used. In addition, when a support is present on the resin layer, the exposure can be performed from the support, or the exposure can be performed after the support is peeled off.

[0434] (Alkali Development Process)

[0435] When there is no support on the resin layer, the portion that has not been photocured (unexposed portion) can be removed by alkali development directly after the exposure step, and then developed to form a pattern of the insulating layer.

[0436] When a support exists on the resin layer, the support is removed after the exposure step, and then the uncured portion (unexposed portion) is removed by alkali development and developed to form a pattern of the insulating layer.

[0437] The unexposed resin layer including the resin composition of the present embodiment contains the compound (C) and thus has excellent alkali developability, and the unexposed resin composition can be removed quickly, thereby obtaining a printed wiring board having a high-definition pattern.

[0438] In the case of alkali development, the developer is not particularly limited as long as it can selectively wash out the unexposed portion, and alkali developers such as tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution can be used. In the present embodiment, tetramethylammonium hydroxide aqueous solution is more preferably used. These alkali developers can be used alone or in combination of two or more.

[0439] In addition, as an alkali development method, for example, it can be carried out by known methods such as dipping, stirring, spraying, shaking dipping, brushing, and scraping. In pattern formation, these development methods can be used in combination as needed. In addition, as a development method, when high-pressure spray is used, the resolution will be further improved, so it is suitable. As the spray pressure when the spray method is adopted, 0.02 to 0.5 MPa is preferred.

[0440] (Post-baking process)

[0441] In this embodiment, after the alkali development step is completed, a post-baking step is performed to form an insulating layer (cured product). As the post-baking step, there can be cited an ultraviolet irradiation step using a high-pressure mercury lamp, a heating step using a clean oven, etc., or these can be used in combination. When irradiating with ultraviolet light, the irradiation amount can be adjusted as needed, for example, 0.05 to 10 J / cm 2 The heating conditions can be appropriately selected as needed, preferably within the range of 150 to 220° C. for 20 to 180 minutes, and more preferably within the range of 160 to 200° C. for 30 to 150 minutes.

[0442] (Conductor layer forming step)

[0443] After the insulating layer (cured product) is formed, a conductor layer is formed on the surface of the insulating layer by dry plating.

[0444] It should be noted that, 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 plasma etching treatment, reverse sputtering treatment, and corona treatment may be used.

[0445] As dry plating, a known metal vapor deposition method such as a vapor deposition method such as PVD (physical vapor deposition) and CVD (chemical vapor deposition), a sputtering method, and an ion plating method can be used.

[0446] In the metal evaporation method, usually, after the surface of the insulating layer is cleaned and activated by a method such as plasma treatment based on oxygen or argon, the metal as the substrate is attached to form a metal layer, and the surface of the metal layer is subjected to secondary evaporation to form a secondary evaporation layer. The thickness of the metal layer is usually 0.001 to 0.1 μm. The thickness of the secondary evaporation layer is usually 0.01 to 0.4 μm. The combined thickness of the metal layer and the secondary evaporation layer is preferably set to 0.5 μm or less. For the metal as the substrate, titanium, zirconium oxide, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten, and alloys of these metals (for example, nickel-chromium alloy) are usually used. As the metal used in the secondary evaporation, copper and nickel can usually be cited. When a highly active metal such as titanium is used as the substrate, nickel or the like can be suitably used as a barrier layer.

[0447] In the present embodiment, it is believed that the imidazole compound (B) has a specific functional group, and the total number of carbon atoms contained in the functional group is more than 8, and the volume is large, so it does not participate in the reaction until the conductor layer forming step, and exists in the insulating layer while maintaining its structure. Therefore, the insulating layer can obtain sufficient adhesion with titanium, zirconium oxide, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten, and alloys of these metals such as titanium and other adhesive metals, especially titanium. Even in a hygroscopic state, the insulating layer is exposed to high temperatures in a reflow process, etc., and can maintain excellent adhesion strength with the conductor layer.

[0448] When using the evaporation method, for example, a multilayer printed circuit board can be placed in a vacuum container, and the metal can be heated and evaporated, thereby forming a base and a secondary evaporation layer on the insulating layer. For the sputtering method, for example, a multilayer printed circuit board can be placed in a vacuum container, an inert gas such as argon gas can be introduced, a DC voltage can be applied, and the ionized inert gas can be collided with the target metal, and the metal collided can form a base and a secondary evaporation layer on the insulating layer.

[0449] Next, a conductor layer is formed on the surface of the secondary vapor-deposited layer by chemical plating, electroplating, etc. The thickness of the conductor layer is usually 0.1 to 20 μm. As a method for subsequent patterning, for example, a subtractive method or a semi-additive method can be used.

[0450] [Semiconductor devices]

[0451] The semiconductor device of the present embodiment includes the resin composition of the present embodiment. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by installing a semiconductor chip in a conductive part of a multilayer printed circuit board. Here, the conductive part is a part of the multilayer printed circuit board that transmits an electrical signal, and its position can be a surface or an embedded part. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

[0452] There is no particular limitation on the method for mounting semiconductor chips when manufacturing semiconductor devices, as long as the semiconductor chips function effectively. Specifically, there are wire bonding mounting methods, flip chip mounting methods, mounting methods based on bumpless build-up layers (BBUL), mounting methods based on anisotropic conductive films (ACF), and mounting methods based on non-conductive films (NCF).

[0453] In addition, a semiconductor device can also 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 a semiconductor chip is mounted can be in the shape of a wafer or a panel. After formation, the same method as the aforementioned multilayer printed circuit board can be used for manufacturing.

[0454] Example

[0455] Hereinafter, the present embodiment will be described in more detail using examples and comparative examples. The present embodiment is not limited at all by the following examples.

[0456] [Synthesis Example 1] Synthesis of Photocuring Initiator (E1)

[0457] As a photocuring initiator (E1), a photocuring initiator (E1) represented by formula (28) was synthesized according to the method described in paragraph

[0344] of Japanese Patent Application No. 2014-500852. 1 H-NMR measurement confirmed that it was a photocuring initiator (E1) represented by formula (28).

[0458] The photocuring initiator (E1) represented by formula (28) is shown below: 1 H-NMR assignment. 1 H-NMR diagram is shown in Figure 1 .

[0459] 1 H-NMR (500MHz, CDCl3) δ (ppm): 9.54 (d, 1H), 8.72 (d, 1H), 8.36 (s, 1H), 8.2 9(s, 1H), 7.79-7.77(m, 2H), 7.61-7.56(m, 3H), 7.25(d, 2H), 7.07(d, 1H), 7.00 (s, 2H), 5.36 (m, 1H), 4.80 (m, 2H), 4.38 (m, 2H), 2.43 (s, 3H), 2.32 (m, 1H), 2.19(s, 6H), 2.07(s, 3H), 1.38-1.22(m, 8H), 0.92(t, 3H), 0.84(t, 3H)

[0460] [Synthesis Example 2] Synthesis of maleimide compound (TMDM)

[0461] The compound (TMDM) represented by formula (19) was synthesized as follows.

[0462] [Synthesis of amido acid compound (hereinafter abbreviated as MA-TMDA)]

[0463] First, MA-TMDA represented by formula (37) was synthesized by the following method.

[0464]

[0465] In a 100 mL four-necked flask equipped with an argon inlet, a Dean-Stark apparatus, a Dimrod cooling tube, 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 stirred at room temperature (25° C.) under an argon gas flow 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)-indane and 6-amino-1,3,3-trimethyl-1-(4-aminophenyl)-indane, manufactured by Nippon Junryo Pharmaceutical Co., Ltd.) and 10 mL of NMP were added to the solution, and stirred at room temperature (25° C.) for 17 hours.

[0466] A portion of the reaction solution was taken out, and water and ethyl acetate were added and shaken. Thereafter, the organic layer was taken out and dried over magnesium sulfate. The solvent of the supernatant was distilled off at 40°C to obtain a yellow oil. 1 H-NMR measurement confirmed that it was MA-TMDA represented by formula (37).

[0467] The following shows the MA-TMDA represented by formula (37): 1 H-NMR assignment. 1 H-NMR diagram is shown in Figure 2 .

[0468] 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)

[0469] 〔Synthesis of TMDM〕

[0470] 0.67 g (3.5 mmol) of p-toluenesulfonic acid monohydrate was added to the above reaction solution, and heated to reflux at 127°C for 2.5 hours. After cooling to room temperature (25°C), the cooled reaction solution was injected into a mixed solution of 50 mL of saturated sodium bicarbonate aqueous solution and 100 mL of ethyl acetate while stirring. Furthermore, 100 mL of water and 100 mL of ethyl acetate were added for stirring and allowed to stand for 5 minutes. Thereafter, the liquid was separated and the aqueous layer was extracted 3 times with 50 mL of ethyl acetate. All the organic layers were combined, washed once with 100 mL of water, once with 10 mL of saturated brine, and twice with 5 mL of saturated brine. Dry with magnesium sulfate, filter out the solid component, and distill the solvent at 40°C to obtain a yellow solid.

[0471] 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 filtered out, 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 it was a maleimide compound (TMDM) represented by formula (19).

[0472] The following shows the TMDM 1 H-NMR assignment. 1 H-NMR diagram is shown in Figure 3 .

[0473] 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)

[0474] [Synthesis Example 3] Synthesis of the compound represented by formula (15)

[0475] The compound (C1) represented by the formula (15) was synthesized as follows.

[0476] In a 200 mL flask, 12.52 g (50 mmol) of di(trihydroxymethyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.), 41.62 g (210 mmol) of cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., H-TMAn-S (trade name)), 6.10 g (50 mmol) of 4-dimethylaminopyridine, 22.26 g of triethylamine, and 150 g of dichloromethane were added, and the mixture was stirred at room temperature (25°C) for 9 hours.

[0477] 200 mL of 10% hydrochloric acid and 200 mL of methyl ethyl ketone were added to the reaction solution, and the mixture was transferred to a separatory funnel. The mixture was washed twice with 100 mL of 10% hydrochloric acid and twice with 150 mL of saturated saline solution, and then dried with magnesium sulfate and the solvent was distilled off. The mixture was vacuum dried at 120°C to obtain 44.00 g of a white solid. The obtained white solid was 1 As a result of H-NMR measurement, it was confirmed to be the compound (C1) represented by formula (15).

[0478] The following shows the compound (C1): 1 H-NMR assignment. 1 H-NMR diagram is shown in Figure 4 .

[0479] 1 H-NMR (500MHz, DMSO-d6) δ (ppm): 12.25 (s, 8H, -COOH), 3.85 (s, 8H), 3.20 (s, 4H), 3.08 (s, 4H), 2.58 (m, 4H), 2.26 (t, 4H), 2.09 (m, 8H), 1.74 (m, 8H), 1.60 (m, 4H), 1.33 (m, 4H), 1.15 (m, 4H), 0.78 (t, 6H)

[0480] In addition, the content of the compound (C1) contained in the reaction solution obtained above was measured by the following method.

[0481] 50 mg of the reaction solution was added to 4500 mg of THF (tetrahydrofuran) as a sample solution, and the solution was subjected to GPC measurement under the following conditions. Based on the obtained elution curve, the peak area was calculated, and the GPC area percentage (content rate) of each component contained in the reaction solution was calculated. It should be noted that the peak area was calculated based on the area between the elution curve and the baseline, and for incompletely separated peaks, it was calculated by vertical segmentation.

[0482] (Measurement conditions)

[0483] Measuring instrument: Prominence (trade name) manufactured by Shimadzu Corporation

[0484] Column: KF-801 (trade name) manufactured by Showa Denko K.K., KF-802 (trade name) manufactured by Showa Denko K.K., KF-803 (trade name) manufactured by Showa Denko K.K., and KF-804 (trade name) manufactured by Showa Denko K.K.

[0485] Flow rate: 1mL / min

[0486] Column temperature: 40°C

[0487] Detector: RI (Refractive Index) detector

[0488] As a result of GPC measurement, the content of the compound (C1) in the reaction solution was 88%.

[0489] [Example 1]

[0490] (Production of resin composition and resin sheet)

[0491] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 5.4 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as an imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 227.0 parts by mass of methyl ethyl ketone (MEK) were added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition). The varnish was dripped onto a PET film (Unipeel (registered trademark) TR1-25 (trade name) manufactured by Unitika Ltd.) having a thickness of 25 μm, and a coating film was formed by spin coating (at 500 rpm for 10 seconds and then at 1000 rpm for 30 seconds). The obtained coating film was dried at 90°C for 5 minutes, and a resin sheet having a resin layer thickness of 5 μm was obtained using the PET film as a support.

[0492] (Preparation of Evaluation Laminated Body)

[0493] The obtained resin sheet was arranged so that the resin surface of the resin sheet was facing the oxide film side of a silicon wafer (manufactured by ADVANTEC CO., LTD., thickness: 525 μm, with oxide film (thickness: 1 μm)), and vacuumed (below 5.0 hPa) for 30 seconds using a vacuum laminator (manufactured by Nikko-Materials Co., Ltd.). Thereafter, the pressure was 10 kgf / cm 2 The laminate molding was performed at a temperature of 100°C for 30 seconds. 2 The stacking molding was performed at a temperature of 100° C. for 60 seconds, thereby obtaining a stacked body for evaluation in which the silicon wafer, the resin layer, and the support were stacked.

[0494] [Example 2]

[0495] As the bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 4.0 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as the imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as the compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 224.4 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0496] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0497] [Example 3]

[0498] As the bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 3.0 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as the imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as the compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 222.5 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0499] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0500] [Example 4]

[0501] As the bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 2.0 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as the imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as the compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 220.7 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0502] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0503] [Example 5]

[0504] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 1.0 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as an imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 218.8 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0505] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0506] [Example 6]

[0507] As the bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 0.5 parts by mass of 2-undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 11) as the imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as the compound (C), and cis, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 217.9 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0508] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0509] [Example 7]

[0510] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 4.95 parts by mass of 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 14) as an imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis-, cis- 1.08 parts by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) as a maleimide compound (D) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.), 15 parts by mass of a compound represented by formula (19) as a maleimide compound (D) (TMDM), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 226.2 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0511] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0512] [Example 8]

[0513] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), as an imidazole compound (B), 1.25 parts by mass of 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 14), as a compound (C), 5.25 parts of a compound (C1) represented by formula (15), and as a cis-, cis- 1.08 parts by mass of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) as a maleimide compound (D) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.), 15 parts by mass of a compound represented by formula (19) as a maleimide compound (D) (TMDM), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 219.3 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0514] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0515] [Example 9]

[0516] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 5.33 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 18) as an imidazole compound (B), 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis-, cis-cyclohexane as a compound (C) as a 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) as a maleimide compound (D) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 226.9 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0517] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0518] [Example 10]

[0519] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), as an imidazole compound (B), 1.0 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 18), as a compound (C), 5.25 parts of a compound (C1) represented by formula (15), and as a cis-, cis-cyclohexane-2-yl group of the compound (C), were prepared. 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) as a maleimide compound (D) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 218.8 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0520] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0521] [Example 11]

[0522] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), as an imidazole compound (B), 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 18), as a compound (C), 5.25 parts of a compound (C1) represented by formula (15), and as a cis-, cis-cyclohexane-2-yl group of the compound (C), were mixed. 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) as a maleimide compound (D) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 217.9 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0523] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0524] [Comparative Example 1]

[0525] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12)) manufactured by Nippon Kayaku Co., Ltd., 5.25 parts by mass of a compound represented by formula (15) (C1) as a compound (C), 1.08 parts by mass of cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a compound (C), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as a photocuring initiator (E) were mixed. 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by BV Co., Ltd., 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 217.0 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0526] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0527] [Comparative Example 2]

[0528] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 2.67 parts by mass of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 3) as an imidazole compound, 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis-, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 221.9 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0529] Precipitation of the resin component occurred in the obtained varnish, and it was impossible to produce a resin sheet and a laminate for evaluation.

[0530] [Comparative Example 3]

[0531] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12) manufactured by Nippon Kayaku Co., Ltd.), 2.85 parts by mass of 2-phenyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 7) as an imidazole compound, 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis-, cis-cyclohexane- 1.08 parts by mass of 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 222.3 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0532] In the obtained varnish, precipitation of the resin component occurred, and it was impossible to produce a resin sheet and a laminate for evaluation.

[0533] [Comparative Example 4]

[0534] 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 1.73 parts by mass of 2-ethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R4 to R7: 2) as an imidazole compound, 5.25 parts of a compound (C1) represented by formula (15) as a compound (C), and cis,cis-cyclohexane-1, 1.08 parts by mass of 2,4-tricarboxylic acid-1,2-anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 220.2 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0535] In the obtained varnish, precipitation of the resin component occurred, and it was impossible to produce a resin sheet and a laminate for evaluation.

[0536] [Comparative Example 5]

[0537] As a bismaleimide compound (A), 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a compound represented by formula (12)) manufactured by Nippon Kayaku Co., Ltd., 5.25 parts by mass of 2,2'-(1,3-phenylene)bis-(2-oxazoline) (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.25 parts by mass of a compound (C1) represented by formula (15) as a compound (C), and cis,cis-cyclohexane-1,2,4-tricarboxylic acid as a compound (C) were prepared. 1.08 parts by mass of 1,2-acid anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts by mass of a compound represented by formula (20) (BCPH01 (trade name) manufactured by Gunei Chemical Industry Co., Ltd.) as a maleimide compound (D), 15 parts by mass of a compound represented by formula (19) (TMDM) as a maleimide compound (D), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM) as a photocuring initiator (E). 1.12 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by Resins BV, 6.38 parts by mass of a compound (E1) represented by formula (28) as a photocuring initiator (E), and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, 226.7 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was heated on a hot plate heated to 90°C to obtain a varnish (resin composition).

[0538] A resin sheet and a laminate for evaluation were obtained by the same method as in Example 1 using the obtained varnish.

[0539] 〔evaluate〕

[0540] The varnish, the resin sheet, and the evaluation laminate were measured and evaluated by the following methods.

[0541] <Varnish appearance>

[0542] The heated varnish was left to stand at room temperature (25° C.) for 1 hour and then cooled. The appearance (state) of the cooled varnish was visually observed and evaluated based on the following criteria.

[0543] "AA": No precipitation and / or gel was generated in the clear coat, showing a transparent appearance.

[0544] "CC": Precipitation and / or gelation occurred in the varnish.

[0545] <Light curing properties>

[0546] Using a Photo DSC (DSC-2500 (trade name) manufactured by TA Instruments Japan Inc.) equipped with a light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (Omnicure (registered trademark) S2000 (trade name) manufactured by U-VIX Corporation), the obtained resin sheet was irradiated with active energy rays having a wavelength of 200 to 600 nm at an illumination of 30 mW and an exposure time of 3.5 minutes to obtain a graph with time (sec) on the horizontal axis and heat flow (mW) on the vertical axis.

[0547] In the obtained graph, the peak area along the horizontal line from the end point of the graph was recorded as enthalpy (J / g). Curability was evaluated according to the following criteria.

[0548] "AA": enthalpy is 1 (J / g) or more.

[0549] "CC": enthalpy is less than 1 (J / g).

[0550] "Unable to measure": No resin sheet was obtained and the measurement was impossible.

[0551] In addition, the enthalpy being 1 (J / g) or more means that curing of the resin is sufficiently advanced by exposure at a predetermined wavelength.

[0552] <Peel Strength>

[0553] The obtained evaluation laminate was irradiated with active energy rays having a wavelength of 200 to 600 nm (MA-20 (trade name) manufactured by MIKASA CO., LTD.) from above the support at an illumination of 18 mW and an irradiation dose of 200 mJ / cm 2 Irradiation includes active energy rays with a wavelength of 200 to 600 nm. Thereafter, using a hot plate heated to 90°C, heating is performed at 90°C for 60 seconds from the silicon wafer surface. Thereafter, cooling is performed to room temperature. Thereafter, the support (PET film) is peeled off and oscillated for 180 seconds in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution (developer, manufactured by Tokuyama Corporation) at 35°C. Thereafter, washing is performed with pure water and air is blown to dry.

[0554] Then, a light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (HMW-201GX (trade name) manufactured by Oku Seisakusho Co., Ltd.) was used at an irradiation dose of 1000 mJ / cm 2 The active energy rays having a wavelength of 200 to 600 nm were irradiated, and then heated at 180° C. for 1 hour to obtain a cured product.

[0555] Thereafter, the surface of the obtained solidified product was subjected to plasma cleaning (400 W, 60 seconds) based on oxygen (O2) using a plasma cleaning machine (PC-1100 (trade name) manufactured by SUMCO). Thereafter, titanium was sputtered on the surface of the cleaned solidified product by a metal vapor deposition method using a sputtering device (QAM-4C-SL (trade name) manufactured by ULVAC) to form a titanium layer (thickness: 50 nm), and copper was sputtered on the surface of the titanium layer to form a copper layer (thickness: 300 nm) as a secondary vapor deposition layer.

[0556] Thereafter, electrolytic copper plating was performed on the surface of the copper layer in such a manner that the copper plating thickness became 18 μm, and the mixture was dried at 180° C. for 1 hour, thereby producing an evaluation wiring board having a titanium layer (thickness: 50 nm), a copper layer (thickness: 300 nm) as a secondary vapor-deposited layer, and a copper-plated layer (thickness: 18 μm) as a conductor layer formed on the solid.

[0557] The obtained evaluation wiring board was used to measure the peel strength of the conductor layer three times according to JIS C6481 "Test methods for copper-clad laminates for printed wiring boards" and the average value (kN / m) was calculated. It should be noted that in Comparative Examples 2 to 4, no evaluation laminate was obtained, and the evaluation wiring board could not be prepared, which was recorded as "unable to measure".

[0558] [Table 1]

[0559]

[0560] As is clear from Table 1, according to this embodiment, even when exposed to any light including active energy rays with a wavelength of 200 to 600 nm, photosensitivity is well generated and photocuring can be performed. According to this embodiment, a cured product having excellent alkali developability is obtained. According to this embodiment, the obtained cured product (insulating layer) has excellent adhesion to adhesive metals such as titanium.

[0561] This application claims priority based on Japanese patent application (Japanese Patent Application No. 2021-099115) filed with the Japan Patent Office on June 15, 2021, the contents of which are incorporated herein by reference.

[0562] Industrial Applicability

[0563] The resin composition of the present embodiment can be suitably used for the preparation of a multilayer printed circuit board, and can be preferably used for the purpose of a resin composition requiring insulation. For example, it can be used in a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, a circuit substrate (laminated board use, multilayer printed circuit board use, etc.), a solder resist, an underfill material, a bonding material, a semiconductor sealing material, a hole-filling resin, and a component embedding resin.

Claims

1. A resin composition comprising a bismaleimide compound (A), an imidazole compound (B), a compound containing one or more carboxyl groups (C) and a photocuring initiator (E), The bismaleimide compound (A) comprises a structural unit represented by the following formula (1) and maleimide groups located at both ends of the molecular chain. In formula (1), R1 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 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, R3 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, and n1 each independently represents an integer of 1 to 10, The imidazole compound (B) comprises at least one selected from the group consisting of 2-undecyl imidazole, 1-(2-cyanoethyl)-2-undecyl imidazole and 2,4,5-triphenyl imidazole, The content of the bismaleimide compound (A) is 30 to 80 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. The content of the imidazole compound (B) is 0.3 to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. The content of the photocuring initiator (E) is 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The content of the compound (C) containing one or more carboxyl groups is 0.1 to 30 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. The compound (C) containing one or more carboxyl groups includes a compound represented by the following formula (3): In formula (3), R8 each independently represents a group represented by the following formula (4) or a hydrogen atom, and R9 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, wherein: At least one R8 is a group represented by the following formula (4), In formula (4), -* represents an atomic bond.

2. The resin composition according to claim 1, further comprising at least one maleimide compound (D) selected from the group consisting of a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), a compound represented by the following formula (8), a compound represented by the following formula (9), and a compound represented by the following formula (10), In formula (5), R 10 , R 11 , and R 12 each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, In formula (6), R 13 , R 14 , and R 15 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, and n2 represents an integer of 1 to 10, In formula (7), R 16 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R 17 each independently represents a hydrogen atom or a methyl group, In formula (8), R 18 Each independently represents a hydrogen atom or a methyl group, n3 represents an integer of 1 to 10, (In formula (9), R 19 each independently represents a hydrogen atom, a methyl group, or an ethyl group, In formula (10), R 20 Each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1-10.

3. A resin sheet comprising: a support, and a resin layer disposed on one or both surfaces of the support, The resin layer comprises the resin composition according to claim 1.

4. The resin sheet according to claim 3, wherein The thickness of the resin layer is 1 to 50 μm.

5. A multilayer printed circuit board comprising: an insulating layer, and a conductor layer formed on one or both sides of the insulating layer, The insulating layer comprises the resin composition according to claim 1. A semiconductor device comprising the resin composition according to claim 1 .

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