TW202415705A - Resin composition, cured product, semiconductor element, and dry film resist - Google Patents

Abstract

The purpose of the present invention is to provide a bismaleimide compound-containing resin composition that can be patterned with light, has a glass transition temperature of 200 DEG C or higher, and has a low dielectric dissipation factor. This resin composition comprises: (A) a bismaleimide compound that is obtained by reacting an aromatic diamine (a-1) represented by formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride and that has a cyclic imide linkage; and (B) a maleimide compound other than the bismaleimide compound (A).

Description

Resin composition, hardener, semiconductor element and dry film resist

The present invention relates to a resin composition containing a bismaleimide compound.

In recent years, electronic devices have been miniaturized and have become more advanced. In multi-layer printed wiring boards, wiring has been required to be miniaturized and denser. Furthermore, in the next generation, materials for high-frequency bands are required, and as a noise countermeasure, transmission loss must be reduced, so the development of insulating materials with excellent dielectric properties is required.

Previously, polyimide resins, polybenzoxazole resins, etc., which are excellent in heat resistance and mechanical properties, have been widely used in surface protection films or interlayer insulating films of semiconductor elements (Patent Document 1). When polyimide resins or polybenzoxazole resins are used as surface protection films or interlayer insulating films, there is a known method of forming through holes by etching using a positive photoresist containing these resins. However, the problem with this method is that complicated steps such as coating or peeling of the photoresist are required. Therefore, with the purpose of rationalizing the working steps, research has been conducted on heat-resistant materials that are given photosensitivity (Patent Document 2). It is known that among these materials, the dielectric properties are not satisfactory for high-frequency band applications represented by the keyword 5th Generation Mobile Communication Technology (5G). In contrast, Patent Document 3 reports that an epoxy resin composition containing an epoxy resin, an active ester compound, and a triazine-containing cresol novolac resin is effective for lowering the dielectric loss tangent, but even for this material, lower dielectric properties are required for high-frequency applications.

On the other hand, Patent Document 4 reports that a resin film containing a resin composition as a non-epoxy material, which contains a bismaleimide resin having a long-chain alkyl group and a hardener, has excellent low dielectric properties.

Furthermore, Patent Documents 5 and 6 disclose polyimide using as raw materials dimer diamines derived from dimer acids, which are dimers of aromatic tetracarboxylic acids and unsaturated fatty acids such as oleic acid, and alicyclic diamines.

In addition, Patent Document 7 discloses a dimaleimide resin having both a long chain aliphatic chain part and an alicyclic structure part, exhibiting a low dielectric loss tangent, and having a glass transition point (Tg) of more than 100°C. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 11-199557 [Patent Document 2] Japanese Patent Publication No. 11-24271 [Patent Document 3] Japanese Patent Publication No. 2011-132507 [Patent Document 4] International Publication No. 2016/114287 [Patent Document 5] Japanese Patent Publication No. 2017-119361 [Patent Document 6] Japanese Patent Publication No. 2019-104843 [Patent Document 7] Japanese Patent Publication No. 2021-123672

[Problems to be solved by the invention] Recent studies have shown that although low molecular weight aromatic maleimide reaches a glass transition temperature (Tg) of more than 200°C, due to its rigid skeleton, the mobility of the reaction site is low, the reactivity under light is very low, and the photopatterning property is low. In addition, it is also known that dimaleimide resins with long-chain alkyl groups have high mobility of the reaction site and good photoreactivity due to their long-chain alkyl groups, and also achieve low dielectric loss tangent, but have low Tg.

Regarding the bismaleimide compound having both a long-chain alkyl group and an alicyclic structure part described in the above-mentioned Patent Document 7, if the ratio of the long-chain alkyl group increases, it becomes very difficult to achieve a high Tg of 200°C or more, and if the ratio of the alicyclic structure part increases, the toughness of the cured film decreases and the crack resistance decreases. Therefore, it is very difficult to achieve a low dielectric loss tangent and a high Tg using only a maleimide resin.

The film described in Patent Document 4 is essentially a combination of a dimaleimide resin having a long-chain alkyl group and a hard low-molecular aromatic maleimide, but the compatibility is poor, and it is easy to produce uneven properties or curing. It is very difficult to achieve a high glass transition temperature (Tg) of 200°C or more required for semiconductor device applications. In addition, the polyimide described in Patent Documents 5 and 6 is difficult to use when curing alone, and has poor compatibility with other resins. In addition, polyimide undergoes closed-loop dehydration during curing, so when laminating a redistribution layer, for example, gaps may be generated and planarization may not be possible depending on the conditions of use.

Therefore, the object of the present invention is to provide a resin composition containing a dimaleimide compound that can be patterned using light, has a glass transition temperature of more than 200°C, and has a low dielectric loss tangent. [Means for Solving the Problem]

In order to solve the above problems, the inventors have repeatedly conducted diligent research and found that the following resin composition containing a bismaleimide compound can achieve the above purpose, thereby completing the present invention.

That is, the present invention relates to the following [1] to [7]. [1] A resin composition comprising: a bismaleimide compound (A) having a cyclic imide bond, obtained by reacting an aromatic diamine (a-1) represented by the following formula (1), a tetrabasic acid dianhydride (a-3) and maleic anhydride; and a maleimide compound (B), at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), and a compound represented by the following formula (8).

[Chemistry 1]

( _R1 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4)

[Chemistry 2]

(In formula (2), R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent; n represents an integer of 1 to 10)

[Chemistry 3]

(In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group; n represents an integer from 1 to 10)

[Chemistry 4]

(In formula (4), R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent)

[Chemistry 5] (In formula (5), _R9 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and _R10 each independently represents a hydrogen atom or a methyl group)

[Chemistry 6] (In formula (6), R ₁₁ each independently represents a hydrogen atom, a methyl group, or an ethyl group)

[Chemistry 7] (In formula (7), R ₁₂ each independently represents a hydrogen atom or a methyl group; n represents an integer from 1 to 10)

[Chemistry 8]

(In formula (8), there are a plurality of _R13 each independently representing a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m represents an integer of 0 to 3; n is a repeated number, the average value of which is 1<n<5) [2] A resin composition comprising: a dimaleimide compound (A) represented by the following formula (9); and a maleimide compound (B), which is at least one selected from the group consisting of a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4), a compound represented by formula (5), a compound represented by formula (6), a compound represented by formula (7), and a compound represented by formula (8).

[Chemistry 9]

(In formula (9), R ₁₆ independently represents a tetravalent organic group containing a cyclic structure; R ₁₅ independently represents a divalent alkyl group having 6 to 200 carbon atoms; R ₁₄ independently represents a tetravalent alkyl group represented by the following formula (10):

[Chemistry 10]

( _R18 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); _R17 is _R14 or _R16 ; m is 1 to 100, and n is 0 to 100; in addition, the order of each repeating unit enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random) [3] The resin composition as described in [1], wherein the tetrabasic acid dianhydride (a-3) comprises the bismaleimide compound (A), and the bismaleimide compound (A) comprises a compound selected from the group consisting of the following formulas (11) to (19).

[Chemistry 11] (In formula (14), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond or the following formula (20)

[Chemistry 12]

=Divalent linking group represented by) [4] The resin composition as described in any one of [1] to [3] further comprises a photocuring initiator (C). [5] A cured product comprising the resin composition as described in any one of [1] to [4]. [6] A semiconductor device comprising a surface protective film, an interlayer insulating film, or an insulating film of a redistribution layer comprising the resin composition containing a bismaleimide compound as described in any one of [1] to [4]. [7] A dry film anticorrosive agent obtained by sandwiching the resin composition containing a bismaleimide compound as described in any one of [1] to [4] with a substrate. [Effect of the invention]

The present invention can provide a resin composition having good light curing properties, a high glass transition temperature (Tg) of 200°C or higher, and a good dielectric loss tangent, and a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device. The resin composition has good light curing properties, a high glass transition temperature (Tg) of 200°C or higher, and a good dielectric loss tangent, and can produce a good resin sheet.

The present invention is described in detail below. The present invention is a resin composition comprising a bismaleimide compound (A) and a maleimide compound (B).

<Bismaleimide compound (A)> The bismaleimide compound (A) of the present invention is a compound having two maleimide groups, and has a cyclic imide bond of an aromatic diamine (a-1) represented by the following formula (1) and a tetrabasic acid dianhydride (a-3). Such a bismaleimide compound (A) is obtained by reacting an aromatic diamine (a-1), a tetrabasic acid dianhydride (a-3) and maleic anhydride. Furthermore, a divalent organic diamine (a-2) having 6 to 200 carbon atoms other than the aromatic diamine (a-1) may also be reacted.

[Chemistry 13]

( _R1 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4)

The bismaleimide compound (I) is a bismaleimide compound represented by the following general formula (2).

[Chemistry 14]

(In formula (2), R ₁₆ independently represents a tetravalent organic group including a cyclic structure; R ₁₅ independently represents a divalent alkyl group having 6 to 200 carbon atoms; R ₁₄ independently represents the following formula (10);

[Chemistry 15]

(R ₁₈ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); R ₁₇ is R ₁₄ or R ₁₅ ; n is 1 to 100, and m is 0 to 100; in addition, the order of each repeating unit enclosed by n and m is not limited, and the bonding pattern may be alternating, block, or random)

In the above formula (1), R ₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl, n-propyl, and isopropyl are more preferred, in terms of excellent adhesion to wafers and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins. Halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, and tert-butoxy. Among these, alkoxy groups having 1 to 4 carbon atoms are preferred, and methoxy, ethoxy, n-propoxy, and isopropoxy are more preferred, in terms of excellent adhesion to chips and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins. As R ₁ , in addition to exhibiting excellent adhesion to chips and substrates, etc., it also exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Preferably, it is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group. More preferably, it is a hydrogen atom, a methyl group, and a hydroxyl group. Still more preferably, it is a hydrogen atom.

In the formula (1), each l independently represents an integer of 1 to 4. As l, in order to exhibit excellent adhesion to a wafer, a substrate, etc., as well as good solubility in a solvent, a low melting point, low water absorption, and good compatibility with other resins, it is preferred that all R _1s are hydrogen atoms, and thus 4 is preferred.

Specific examples of the aromatic diamine (a-1) represented by the formula (1) include aromatic diamines such as m-xylylenediamine (the following formula (25)), p-xylylenediamine (the following formula (26)), and o-xylylenediamine (the following formula (27)). As a commercial product, m-xylylenediamine (MXDA: manufactured by Mitsubishi Gas Chemical Co., Ltd.) can be easily obtained. As the aromatic diamine (a-1) represented by the formula (1), m-xylylenediamine (the following formula (25)) is preferred.

[Chemistry 16]

[Chemistry 17]

[Chemistry 18]

The bismaleimide compound (A) is not particularly limited as long as it can exert the effects of the present invention, but in terms of good solubility in solvents, low melting point, low water absorption and good compatibility with other resins, the weight average molecular weight is preferably 100 to 100,000, more preferably 500 to 30,000. In addition, in this embodiment, the so-called "weight average molecular weight" refers to the weight average molecular weight obtained by gel permeation chromatography (GPC) and converted to polystyrene standards.

Generally, maleimide compounds have poor light transmittance. Therefore, if the resin composition described later contains the maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator is difficult to generate free radicals. Therefore, generally speaking, the photoradical reaction of the maleimide compound is difficult to proceed, and even if the free radical polymerization or dimerization reaction of the maleimide monomer proceeds, its reactivity is very low. However, the dimaleimide compound (A) has very excellent light transmittance because the maleimide group is bonded to the aromatic ring via the methylene group and the conjugation length is short. Therefore, light sufficiently reaches the photocuring initiator, thereby efficiently inducing the photoradical reaction of the maleimide. Furthermore, when a chloroform solution containing the maleimide compound at 1 mass% is prepared and the light transmittance of the chloroform solution is measured using light having a wavelength of 405 nm (h-ray), the transmittance is 3% or more, showing very excellent light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, the photo-radical reaction of the maleimide is efficiently induced even when an active energy ray containing a wavelength of 405 nm (h-ray) is used.

When active energy rays including a wavelength of 405 nm (h-rays) are used, if the photocuring initiator does not absorb the light of the wavelength of 405 nm (h-rays) and generate free radicals, polymerization does not proceed. Therefore, in this case, as the photocuring initiator described later, it is preferable to use a photocuring initiator having an absorbance of 0.1 or more at a wavelength of 405 nm (h-rays) and showing very excellent absorption of light at a wavelength of 405 nm (h-rays).

Since the bismaleimide compound (A) has excellent light transmittance as described above, for example, when light with a wavelength of 405 nm is used, the light also fully reaches the photocuring initiator, and the free radicals generated by the photocuring initiator are used to perform a free radical reaction, and photocuring can also be performed in a resin composition containing a large amount of maleimide compounds. Moreover, the cured product obtained by including the resin composition of this embodiment has excellent light curing property, heat resistance and thermal stability, so a protective film and an insulating layer can be appropriately formed.

In addition, the bismaleimide compound (A) may have a structure derived from a divalent organic diamine (a-2) other than the aromatic diamine (a-1). The divalent organic diamine (a-2) other than the aromatic diamine (a-1) used for the synthesis of the bismaleimide compound (A) is independently a divalent hydrocarbon group having 6 to 200 carbon atoms, preferably 8 to 100 carbon atoms, and more preferably 10 to 50 carbon atoms. Among them, it is preferably a branched divalent hydrocarbon group in which one or more hydrogen atoms in the divalent hydrocarbon group are substituted by an alkyl or alkenyl group having 6 to 200 carbon atoms, preferably 8 to 100 carbon atoms, and more preferably 10 to 50 carbon atoms. The branched divalent hydrocarbon group may be any of a saturated aliphatic hydrocarbon group and an unsaturated hydrocarbon group, and may have an alicyclic structure or an aromatic ring structure in the middle of the molecular chain. Specifically, the branched divalent hydrocarbon group may be a hydrocarbon group derived from diamines at both ends called dimer diamines. The so-called dimer diamines, as shown in the following formulas (28) to (33), are obtained by replacing two carboxyl groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, with primary amine groups (see Japanese Patent Laid-Open No. 9-12712, etc.). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.) having a diamine with a C36 skeleton as the main component, and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These can be used alone or in combination of two or more. The following is a non-limiting general formula of dimer diamine (in each formula, m+n=6 to 17 is preferred, p+q=8 to 19 is preferred, and the dotted line portion indicates a carbon-carbon single bond or a carbon-carbon double bond). The main component of PRIAMINE 1074 and PRIAMINE 1075, i.e., the diamine having a C36 skeleton, satisfies the relationship of m+n+p+q+13=36 in the following general formulas (28) to (31) of the dimer diamine, and satisfies the relationship of m+n+p+q+5=36 in the following general formulas (32) and (33) of the dimer diamine.

[Chemistry 19]

The tetrabasic acid dianhydride (a-3) used for the synthesis of the bismaleimide compound (A) is not particularly limited as long as it has two acid anhydride groups in one molecule. Specific examples of the component (a-3) include pyromellitic anhydride, ethylene glycol-bis(trimellitic anhydride), glycerol-bis(trimellitic anhydride) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonic acid tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, biscyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and biscyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-bisphenol A dianhydride, and the like. Among them, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 4,4'-bisphenol A dianhydride are preferred in terms of solvent solubility and adhesion to the substrate. These may be used alone or in combination of two or more.

From the viewpoint of the solvent solubility of the finally obtained bismaleimide resin, the tetrabasic acid dianhydride (a-3) used for the synthesis of the bismaleimide compound (A) is preferably a compound selected from the group consisting of the following formulas (11) to (19).

[Chemistry 20]

In formula (14), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (20).

[Chemistry 21]

In the present invention, the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (34).

[Chemistry 22]

In the present invention, the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (35).

[Chemistry 23]

In the present invention, the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (36).

[Chemistry 24]

In the present invention, the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (37).

[Chemistry 25]

In the present invention, the tetrabasic acid dianhydride (a-3) is preferably a tetrabasic acid dianhydride (a-3) represented by the following general formula (38).

[Chemistry 26]

Furthermore, the bismaleimide compound (A) may be a bismaleimide compound obtained by reacting the aromatic diamine (a-1), an organic diamine (a-2) other than the aromatic diamine (a-1), the tetracarboxylic dianhydride (a-3), and the maleic anhydride. By copolymerizing the organic diamine (a-2) other than the aromatic diamine (a-1), the light curing property and the anti-cracking property of the obtained cured product can be further improved, and the required physical properties can be controlled as required.

The organic diamine (a-2) other than the aromatic diamine (a-1) (hereinafter referred to as the organic diamine (a-2) as appropriate) in the present invention refers to a diamine other than the diamine contained in the aromatic diamine (a-1). Such organic diamine (a-2) is not particularly limited, and examples thereof include: aliphatic diamines such as 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, and norbornene diamine; 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, 1,3- Aromatic diamines such as bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, and 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylsulfone; 3,3'-diaminodiphenylsulfone; 4,4-diaminobenzophenone; 4,4-diaminodiphenylsulfide; and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Of these, aliphatic diamines having 6 to 12 carbon atoms such as 1,6-hexamethylenediamine; and diaminocyclohexanes such as 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, and norbornenediamine are more preferred from the viewpoint of obtaining a cured product having high heat resistance. When the bismaleimide compound (A) of the present invention is obtained using these organic diamines (a-2), one of these organic diamines (a-2) may be used alone, or two or more of them may be used in combination.

In the resin composition, the content of the dimaleimide compound (A) is preferably 10 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 60 to 80 parts by mass, based on 100 parts by mass of the total of the dimaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving compatibility with the maleimide compound (B) described later, obtaining better heat resistance and thermal stability, and further obtaining a resin composition having good light curing properties and crack resistance.

<Method for producing bismaleimide compound (A)> The method for producing the bismaleimide compound (A) is not particularly limited, and it can be produced efficiently by, for example, the method shown below. As a basic process, through step A of synthesizing acylamine using tetrabasic acid dianhydride and diamine, and performing ring-closure dehydration, then reacting maleic anhydride to synthesize maleic acid, and finally performing ring-closure dehydration to cap the molecular chain end with maleimide group, step B, thereby obtaining a bismaleimide compound.

In the production method, each step can be roughly divided into two types: the synthesis reaction of acylamine or maleic acid and the ring-closing dehydration reaction, which are described in detail below.

In step A, first, acylamine is synthesized by reacting a specific tetrabasic acid dianhydride with a specific diamine. The reaction is generally carried out in an organic solvent (e.g., a nonpolar solvent or a high-boiling-point aprotic polar solvent) at room temperature (25°C) to 100°C. Then, the ring-closing dehydration reaction of acylamine is carried out at 90°C to 120°C while removing the water produced as a by-product of the condensation reaction from the system. In order to promote the ring-closing dehydration reaction, an organic solvent (e.g., a nonpolar solvent, a high-boiling-point aprotic polar solvent, etc.) or an acid catalyst may be added.

As organic solvents, toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. can be listed. These can be used alone or in combination of two or more. In addition, as acid catalysts, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. can be listed. These can be used alone or in combination of two or more. The molar ratio of diamine to tetrabasic acid dianhydride is preferably set to diamine/tetrabasic acid dihydrate = 2.5 to 1.02/1.0, and more preferably set to diamine/tetrabasic acid dianhydride = 2.0 to 1.15/1.0. By mixing at this ratio, a copolymer containing amino groups at both ends can be synthesized.

In step B, maleic acid is synthesized by reacting the diamine having amino groups at both ends obtained in step B with maleic anhydride at room temperature (25°C) to 100°C, and finally, the water in the system generated as a by-product under the condition of 95°C to 120°C is removed and closed-loop dehydration is performed, thereby using maleimide groups to cap the ends of the molecular chain, and the target bismaleimide compound can be obtained. If the capping reaction of the ends of the molecular chain using maleimide groups is performed below 120°C, it is difficult to produce side reactions or high molecular weight bodies, so it is better. If this manufacturing method is used, the obtained bismaleimide compound has a block copolymer structure, so it can be uniform and improve the compatibility of the synthesized resin.

The compound of the present invention may be purified by a conventional method, and reprecipitation or the like may be used.

The mixing ratio of the raw materials in the reaction is preferably such that (the total molar number of the aromatic diamine (a-1) and the organic diamine (a-2)): (the total molar number of the tetracarboxylic dianhydride (a-3) + 1/2 of the molar number of maleic anhydride) is 1:1. In addition, when the organic diamine (a-2) is used, from the viewpoint of the tendency to obtain a composition with better photocurability, the ratio of (the molar number of the organic diamine (a-2)): (the molar number of the aromatic diamine (a-1)) is preferably 0.1 or more, and more preferably 0.3 or more. Furthermore, when the organic diamine (a-2) is used, the polymerization form of the amide unit comprising the aromatic diamine (a-1) and the tetracarboxylic dianhydride (a-3) and the amide unit comprising the organic diamine (a-2) and the tetracarboxylic dianhydride (a-3) may be random polymerization or block polymerization.

<Maleimide compound (B)> The resin composition contains a maleimide compound (B) (also referred to as component (B)) other than the dimaleimide compound (A). The maleimide compound (B) is at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), and a compound represented by the following formula (8). The maleimide compound (B) may be used in combination with one or more of the compounds represented by the following formulas (2) to (8). In addition, in order to obtain a resin sheet having better solubility of the bismaleimide compound (A) and the maleimide compound (B), better photocurability and suppressed cracking, the resin composition described below preferably contains one to two compounds represented by the following formula (2) to formula (8) as the maleimide compound (B), and more preferably contains one compound as the maleimide compound (B).

As described above, maleimide compounds generally have very low photoradical reactivity. However, as described above, the bismaleimide compound (A) has very excellent light transmittance. Therefore, by using the maleimide compound (B), the photocuring initiator (C) described below, and the compound (D) containing one or more carboxyl groups described below together with the bismaleimide compound (A), light can fully reach the photocuring initiator, and the photoradical reaction of the maleimide can be efficiently induced, and photocuring can be performed using various active energy rays.

Since the bismaleimide compound (A) has excellent light transmittance, for example, even when an active energy line having a wavelength of 365 nm or an active energy line having a wavelength of 405 nm is used, the light can fully reach the photocuring initiator, and the free radicals generated by the photocuring initiator are used to perform a free radical reaction, and photocuring can also be performed in the composition containing the maleimide compound (B). In addition, the maleimide compound (B) has good compatibility with the bismaleimide compound (A) and has excellent solubility in organic solvents. The obtained cured product has excellent heat resistance, photocurability and thermal stability, so the resin composition of this embodiment can appropriately form a protective film and a redistribution layer.

Next, the compounds represented by the following formula (2) to formula (8) contained in the maleimide compound (B) are described. (Compound represented by formula (2)) The compound represented by formula (2) is the following compound.

[Chemistry 27]

In formula (2), R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. n represents an integer of 1 to 10. As the linear or branched alkyl group having 1 to 6 carbon atoms, from the viewpoint of exhibiting good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a methyl group is more preferred. In addition, among R ₂ , R ₃ , and R ₄ , from the viewpoint of exhibiting more excellent solubility in solvents, it is preferred that R ₂ and R ₄ are linear or branched alkyl groups having 1 to 6 carbon atoms, and R ₃ is a hydrogen atom. The preferred alkyl group is as described above. From the viewpoint of excellent solubility in the solvent, obtaining a more suitable viscosity, and further controlling the viscosity increase of the varnish, n is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

As the compound represented by formula (2), commercially available products may be used, for example, BCPH13 (trade name) manufactured by Qun Young Chemical Co., Ltd. represented by formula (39), BCPH01 (trade name) manufactured by Qun Young Chemical Co., Ltd., or BMC X426 (trade name) manufactured by Qun Young Chemical Co., Ltd. represented by formula (40).

[Chemistry 28]

In formula (39), n is an integer ranging from 1 to 5.

[Chemistry 29]

In formula (40), n is an integer ranging from 1 to 10.

(Compound represented by formula (3)) The compound represented by formula (3) is the following compound.

[Chemistry 30]

In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 to 10. As the maleimide compound represented by formula (3), commercially available products can be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by formula (41) can be mentioned.

[Chemistry 31]

In formula (41), n is an integer ranging from 1 to 10.

(Compound represented by formula (4)) The compound represented by formula (4) is the following compound.

[Chemistry 32]

In formula (4), R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent. The linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, and heptyl. The hydrogen atom in these alkyl groups may be substituted by a halogen atom such as a fluorine atom or a chlorine atom, or a cyano group. Among these alkyl groups, methyl, ethyl, isopropyl, and t-butyl are preferred, methyl, ethyl, and t-butyl are more preferred, and methyl is further preferred. As the compound represented by formula (4), the compound represented by formula (42) (also referred to as TMDM in this embodiment) is further preferred, in terms of having better photocurability, heat resistance, and thermal stability, and having better solubility in a solvent.

[Chemistry 33]

(Compound represented by formula (5)) The compound represented by formula (5) is the following compound.

[Chemistry 34]

In formula (5), _R9 each independently represents a hydrogen atom, a methyl group or an ethyl group, and _R10 each independently represents a hydrogen atom or a methyl group. As _R9 , from the viewpoint of showing good solubility in solvents, a low boiling point, low water absorption, and good compatibility with other resins, a methyl group or an ethyl group is preferred. As _R10 , from the viewpoint of showing good solubility in solvents, a low boiling point, low water absorption, and good compatibility with other resins, a hydrogen atom is preferred.

As the maleimide compound represented by formula (5), a commercially available product can be used, for example, BMI-70 (trade name) manufactured by K.I Chemical Co., Ltd. represented by formula (43) can be mentioned.

[Chemistry 35]

(Compound represented by formula (6)) The compound represented by formula (6) is the following compound.

[Chemistry 36]

In formula (6), R ₁₁ each independently represents a hydrogen atom, a methyl group or an ethyl group. As R ₁₁ , a methyl group or an ethyl group is preferred from the viewpoint of exhibiting good solubility in solvents, a low boiling point, low water absorption, and good compatibility with other resins. As the maleimide compound represented by formula (6), commercially available products may be used, for example, BMI-80 (trade name) manufactured by KI Chemical Co., Ltd. represented by formula (44) may be cited.

[Chemistry 37]

(Compound represented by formula (7)) The compound represented by formula (7) is the following compound.

[Chemistry 38]

In formula (7), R ₁₂ each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 to 10. As R ₁₂ , a hydrogen atom is preferred from the viewpoint of exhibiting good solubility in a solvent, a low boiling point, low water absorption, and good compatibility with other resins. As n, an integer of 1 to 5 is more preferred from the viewpoint of excellent solubility in a solvent, obtaining a more suitable viscosity, and being able to further control the viscosity increase of the varnish.

As the maleimide compound represented by formula (7), a commercially available product may be used, for example, BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. represented by formula (45) may be mentioned.

[Chemistry 39]

In formula (45), n is an integer from 1 to 5.

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

[Chemistry 40] (In formula (8), the presence of a plurality of R ₁₃ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m represents an integer of 0 to 3; n is a repeated number, and its average value is 1<n<5)

In formula (8), m is usually 0 to 3, preferably 0 to 2, and more preferably 0. _R13 is usually a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom. When m is greater than 3 or when _R13 is an alkyl group having 6 or more carbon atoms, the electrical properties may be degraded due to molecular vibration when the alkyl group is exposed to high frequencies.

The compound (8) is more preferably a structure represented by the following formula (46). This is because, in the formula (8), when R is an alkyl group having 1 to 5 carbon atoms, the substitution position of the propyl group with respect to the benzene ring to which the maleimide group is not bonded decreases the crystallinity compared to when it is the para position.

[Chemistry 41]

(In formula (46), the presence of a plurality of R ₂₃ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m represents an integer of 0 to 3; n is a repeated number, and its average value is 1<n<5)

The preferred ranges of R ₂₃ and m in formula (46) are the same as those in formula (8).

In the resin composition, the content of the maleimide compound (B) is preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total of the dimaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving compatibility with the dimaleimide compound (A), obtaining better heat resistance and thermal stability, and further obtaining a resin composition having good light curing properties and crack resistance.

The bismaleimide resin (A) and the maleimide resin (B) are characterized by excellent compatibility. In the present application, "compatible" means that when a curable resin composition is formed by uniformly mixing two or more resins, the haze of the solution is less than 50 when in a liquid state, and when a cured product is formed, only one glass transition temperature (Tg) of the curable resin composition is measured. In other words, in the "incompatible" state, the haze is 50 or more when in a liquid state, and in the cured product, multiple Tgs can be measured even if the resins are uniformly mixed.

The compatibility and haze of the curable resin composition of the present invention are measured as follows. [Compatibility] When visually observing the curable resin composition, the one that has no precipitates and can be applied to the substrate is considered to have good compatibility, and the one that has precipitates and is difficult to apply to the substrate is considered to have poor compatibility. [Haze value] According to Japanese Industrial Standards (JIS) K7136, the total light transmittance (Tt) is calculated by the following calculation formula (1) based on the ratio of the total light transmittance (Tt) and the diffuse light transmittance (Td) diffused and transmitted through the sheet. The total light transmittance (Tt) represents the total amount of light that passes through the curable resin composition when the curable resin composition is placed in an angle unit with an optical path length of 10 mm and irradiated with light using a color/turbidity simultaneous measuring instrument (Nippon Denshoku Co., Ltd., COH400) at 25°C. The total light transmittance (Tt) is the sum of the parallel light transmittance (Tp) that passes through in a coaxial state with the incident light and the diffuse light transmittance (Td). Fog density (H) = Td/Tt×100  ···(1)

<Photopolymerization initiator (C)> As the photopolymerization initiator (C), there is no particular limitation, and previously used photopolymerization initiators can be appropriately adopted, for example: acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, michler's ketone, dibenzodione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin Dimethyl benzoyl ketal, thioanthrone, 2-chlorothioanthrone, 2-methylthioanthrone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one , 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-pyropropane-1-one, 2-benzyl-2-dimethylamino-1-(4-pyrophenyl)-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-oxy Photopolymerization initiators such as phosphine, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzyl oxime), acetone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), and 2,4-dimethylthioanthrone can be used. As such a photopolymerization initiator (C), one type can be used alone or two or more types can be used in combination.

Among these, as the photopolymerization initiator (C), from the viewpoint of forming a fine pattern using a reduced projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm) which is standardly used in the production step of a semiconductor protective film, it is preferred to use a photopolymerization initiator that efficiently generates free radicals at an exposure wavelength of 310 nm to 436 nm (more preferably 365 nm). In addition, maleimide groups generally do not homopolymerize using free radicals, but mainly react with free radicals generated by the photopolymerization initiator to form a cross-linked structure by dimerization of the bismaleimide compound. Therefore, the inventors of the present invention speculate that the bismaleimide compound is apparently less reactive than acrylic compounds, etc., which are generally used as photopolymerizable compounds. Therefore, from the viewpoint of generating radicals more efficiently and increasing the reactivity at an exposure wavelength of 310 nm to 436 nm (more preferably 365 nm), the photopolymerization initiator of the present invention is preferably a compound having an oxime structure or a thioxanthrone structure.

Examples of such photopolymerization initiators include 1,2-octanedione having an oxime structure, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)] (manufactured by BASF Japan, "IRGACURE OXE-01"), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE-02"), and 2,4-dimethylthioanthrone having a thioxanthrone structure (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"). Such a photopolymerization initiator having a high ability to generate free radicals by light tends to have too high a reactivity and be difficult to control the reaction when used for the photopolymerization of a general acrylic compound or the like, but can be suitably used in the present invention.

In the resin composition, the content of the photocuring initiator (C) 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 based on 100 parts by mass of the total of the dimaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving the compatibility with the dimaleimide compound (A) and the maleimide compound (B), allowing the photocuring to proceed sufficiently, making the exposed portion sufficiently insolubilized in terms of the developability in an organic solvent, and obtaining a resin sheet with suppressed cracking.

<Compound (D) containing one or more carboxyl groups> The resin composition may contain a compound (D) containing one or more carboxyl groups (also referred to as component (D) or compound (D)). The compound (D) is not particularly limited as long as it contains one or more carboxyl groups in the compound. The carboxyl group may be a salt such as a sodium salt or a potassium salt. When the molecule contains two or more carboxyl groups, it may be an acid anhydride formed by the mutual linkage of these groups. The compound (D) may be used alone or in combination of two or more.

Various active energy rays can be used to photoharden the compound (D) together with the dimaleimide compound (A) and the maleimide compound (B) and the photohardening initiator (C) as required to obtain a hardened material. In addition, a resin composition containing the compound (D) can be obtained in the unexposed portion. When a 1% by mass N-methylpyrrolidone solution containing the compound (D) is prepared and the transmittance of the 1% by mass N-methylpyrrolidone solution containing the compound (D) is measured using an active energy ray having a wavelength of 365 nm (i-ray), the transmittance of the compound (D) is preferably 5% or more. Thus, the compound (D) shows very excellent light transmittance. In addition, when the transmittance of a 1 mass % N-methylpyrrolidone solution containing the compound (D) is measured using active energy rays containing a wavelength of 405 nm (h-rays), the transmittance is preferably 5% or more, which also shows very excellent light transmittance. If such a compound (D) is used, for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, a photoradical reaction of maleimide is efficiently induced even when active energy rays containing a wavelength of 405 nm (h-rays) are used. For a resin composition having better photocurability, the preferred range of transmittance at a wavelength of 365 nm (i-rays) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. For a resin composition that can obtain better photocurability, the preferred range of transmittance at a wavelength of 405 nm (h-ray) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more. Furthermore, 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.

In the present embodiment, from the viewpoint of obtaining more excellent alkali developing property, it is preferred that the compound (D) contains 2 to 4 carboxyl groups in the molecule.

The molecular weight of the compound (D) is preferably 50 to 1,000, more preferably 100 to 800, from the viewpoint of further improving the developing property.

Examples of the compound (D) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, and hetero compounds containing one or more carboxyl groups. These compounds (D) may be used alone or in combination of two or more.

(Aliphatic compounds containing one or more carboxyl groups) Examples of aliphatic compounds containing one or more carboxyl groups include chain aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, chain aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may also have hydrogen atoms, and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups in the molecule. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by these groups being linked to each other. When these compounds have carboxylalkyl groups in the molecule, they may be acid anhydrides formed by carboxylalkyl groups and carboxyl groups being linked to each other. When these compounds have two or more carboxylalkyl groups in the molecule, they may be acid anhydrides formed by these groups being linked to each other.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-hexyl, and 2-methylpropoxy. Examples of the aryloxy group include phenoxy and p-tolyloxy. Examples of the aryl group include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthracenyl. Examples of the aminoalkyl group include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl. Examples of carboxyalkyl groups include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl.

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, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

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.

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 propane diacid, octanedioic acid, nonane diacid, decane diacid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

Examples of the alicyclic polycarboxylic acid include carboxylic acids obtained by further adding one or more carboxyl groups to an alicyclic monocarboxylic acid. Examples include cyclopropane dicarboxylic acid, cyclopropylene dicarboxylic acid, cyclopropane tricarboxylic acid, cyclopropylene tricarboxylic acid, cyclobutane dicarboxylic acid, cyclobutene dicarboxylic acid, cyclobutane tricarboxylic acid, cyclobutene tricarboxylic acid, cyclobutane tetracarboxylic acid, cyclobutene tetracarboxylic acid, cyclopentane dicarboxylic acid, cyclopentene dicarboxylic acid, cyclopentane tricarboxylic acid, cyclopentene tricarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentene tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclopent ... Monocyclic carboxylic acids such as hexanedicarboxylic 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; polycyclic or bridged aliphatic ring dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid, etc.

(Aromatic compounds containing one or more carboxyl groups) Examples of the parent skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenylacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, and anthracene pentacarboxylic acid. Aromatic compounds may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxyalkyl groups on the aromatic rings of these parent skeletons. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the mutual linkage of these groups. When these compounds have carboxyalkyl groups in the molecule, they may be acid anhydrides formed by the mutual linkage of carboxyalkyl groups and carboxyl groups. When these compounds have two or more carboxyalkyl groups in the molecule, they may also be acid anhydrides formed by the mutual linkage of these groups. For these substituents, please refer to the above description.

(Hetero compounds containing one or more carboxyl groups) As the parent skeleton of the hetero compound containing one or more carboxyl groups, for example, there can be listed compounds containing one or more carboxyl groups in hetero rings such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thione, phenothiazine, phenothiazine, xanthine, acridine, phenazine, and carbazole. The hetero compound may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups on these parent skeletons. In addition, when these compounds have two or more carboxyl groups in the molecule, they may also be acid anhydrides formed by the mutual linkage of these groups. When these compounds have a carboxyalkyl group in the molecule, they may also be an acid anhydride formed by the carboxyalkyl group and the carboxyl group being linked to each other. When these compounds have two or more carboxyalkyl groups in the molecule, they may also be an acid anhydride formed by the carboxyalkyl group and the carboxyl group being linked to each other. For these substituents, please refer to the above description.

As compound (E), from the perspective of imparting better alkali development properties to the resin composition, preferred are compounds represented by formula (21), compounds represented by formula (22), compounds represented by formula (23), and compounds represented by formula (24). From the perspective of imparting better alkali development properties to the resin composition, preferred is the compound represented by formula (23).

The compound represented by formula (21) is as follows.

[Chemistry 42]

In formula (21), R ₁₉ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an aminomethyl group. In addition, when the compound represented by formula (21) has two or more carboxyl groups, it may also be an acid anhydride formed by these groups being linked to each other. In formula (21), the upper limit of the number of carboxyl groups is 6. In terms of alkali development, R ₁₉ is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferably to contain a carboxyl group. Furthermore, benzoic acid tends to have poor alkali development compared to other compounds (D) containing one or more carboxyl groups. In addition, o each independently represents an integer of 1 to 5.

As the compound represented by the formula (21), the compound represented by the formula (47) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 43]

In formula (47), R ₁₉ each independently represents a hydrogen atom, a hydroxyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, R ₁₉ is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, o each independently represents an integer from 0 to 4. The number of carboxyl groups s represents an integer from 5 to o. In terms of showing better alkali development, the number of carboxyl groups s is preferably an integer from 1 to 3. In this case, the number o of R ₁₉ is an integer from 5 to s and is an integer from 2 to 4. The compound represented by formula (47) contains two or more carboxyl groups, and may also be an acid anhydride formed by these groups being linked to each other.

Examples of the compound represented by formula (21) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof. Examples of the anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. As the compound represented by formula (21), phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof are preferred in terms of obtaining better alkali developing properties.

The compound represented by formula (22) is as follows.

[Chemistry 44]

In formula (22), R ₂₀ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. In addition, when the compound represented by formula (22) has two or more carboxyl groups, these groups may be linked to each other to form an acid anhydride. In formula (22), the upper limit of the number of carboxyl groups is 10. When the compound represented by formula (22) has a carboxymethyl group, it may be an acid anhydride formed by a carboxymethyl group and a carboxyl group linked to each other. In terms of alkali development, R ₂₀ is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferably to include a carboxyl group. In addition, p each independently represents an integer of 1 to 9.

When R ₂₀ contains a carboxyl group, the number p of the carboxyl groups is preferably 1 to 3 from the viewpoint of alkali developability. R ₂₀ other than the carboxyl group is preferably independently a hydrogen atom or a hydroxyl group, more preferably a hydrogen atom. When the compound represented by formula (22) contains 1 to 3 carboxyl groups, the number of R ₂₀ other than the carboxyl group is 7 to 9.

Examples of the compound represented by formula (22) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic anhydride.

The compound represented by formula (23) is as follows.

[Chemistry 45]

In formula (23), R ₂₁ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. In addition, when the compound represented by formula (23) has two or more carboxyl groups, these groups may be linked to each other to form an acid anhydride. In formula (23), the upper limit of the number of carboxyl groups is 10. When the compound represented by formula (23) has a carboxymethyl group, it may be an acid anhydride formed by a carboxymethyl group and a carboxyl group linked to each other. In terms of alkali development, R ₂₁ is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferably to contain a carboxyl group. In addition, q each independently represents an integer of 1 to 9.

As the compound represented by the formula (23), the compound represented by the formula (48) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 46]

In formula (48), R ₂₁ each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, R ₂₁ is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, q each independently represents an integer from 0 to 8. The number of carboxyl groups t represents an integer from 9 to q. In terms of showing better alkali development, the number of carboxyl groups t is preferably an integer from 1 to 3. In this case, the number q of R ₂₁ is an integer from 9 to t and is an integer from 6 to 8. The compound represented by formula (48) contains two or more carboxyl groups, and may also be an acid anhydride formed by these groups being linked to each other. When the compound represented by formula (48) has a carboxymethyl group, the carboxymethyl group and the carboxyl group may be linked to each other to form an acid anhydride.

Examples of the compound represented by formula (23) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. In terms of obtaining better alkali developing properties, the compound represented by formula (23) is preferably cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

The compound represented by formula (24) is as follows.

[Chemistry 47]

In formula (24), R ₂₂ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, when the compound represented by formula (24) has one or more carboxyl groups, it may be an acid anhydride formed by a carboxylmethyl group and a carboxyl group linked to each other. In addition, when the compound represented by formula (24) has two or more carboxyl groups, it may be an acid anhydride formed by these groups linked to each other. In formula (24), the upper limit of the number of carboxyl groups is 5. In formula (24), when the compound represented by formula (24) has two or more carboxylmethyl groups, it may be an acid anhydride formed by these groups linked to each other. In formula (24), the upper limit of the number of carboxyl groups is 6. In terms of alkali developability, _R22 is preferably independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amine group, and more preferably contains a carboxyl group in terms of obtaining better alkali developability. In addition, r is independently an integer of 1 to 5.

As the compound represented by the formula (24), the compound represented by the formula (49) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 48]

In formula (49), R ₂₂ each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, R ₂₂ is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, r each independently represents an integer of 0 to 4. The number of carboxyl groups u represents an integer of 5-r. In terms of showing better alkali development, the number of carboxyl groups u is preferably an integer of 1 to 3. In this case, the number r of R ₇ is an integer of 5-u and an integer of 2 to 4. In formula (49), it may be an acid anhydride formed by the carboxymethyl group and the carboxyl group being linked to each other. When the compound represented by formula (49) has two or more carboxyl groups, it may also be an acid anhydride formed by the two groups being linked to each other. In formula (49), the upper limit of the number of carboxyl groups is 5. When the compound represented by formula (49) has two or more carboxymethyl groups, these groups may be linked to each other to form an acid anhydride. In formula (49), the upper limit of the number of carboxymethyl groups is 6.

Examples of the compound represented by formula (24) include phenylene acetic acid, 1,2-phenylene diacetic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and anhydrides thereof. Examples of the anhydrides thereof include 1,2-phenylene diacetic acid anhydride. As the compound represented by formula (24), 1,2-phenylene diacetic acid is preferred in terms of obtaining better alkali development properties.

The compounds (D) containing one or more carboxyl groups may be used alone or in combination of two or more.

In the resin composition, the content of the compound (D) having one or more carboxyl groups is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass based on 100 parts by mass of the total of the dimaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving compatibility with the dimaleimide compound (A) and the maleimide compound (B), further reducing the liquid component in the varnish, and providing better alkali developing properties.

<Compound (E) Reactive with Maleimide Groups Other Than the Dimaleimide Compound (A) and the Maleimide Compound (B)> The resin composition may contain maleimide compounds other than the dimaleimide compound (A) and the maleimide compound (B), cyanate compounds, phenol resins, epoxy resins, cyclohexycyclobutane resins, benzoxazine compounds, carbodiimide compounds, and compounds having ethylenically unsaturated groups as compounds (E) reactive with maleimide groups other than the dimaleimide compound (A) and the maleimide compound (B).

(Maleimide compounds other than the bismaleimide compound (A) and the maleimide compound (B)) The other maleimide compound is not particularly limited as long as it is a compound other than the bismaleimide compound (A) and the maleimide compound (B) and has one or more maleimide groups in the molecule. Specific examples thereof 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-5-methyl)- -4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bisconimide, m-phenylene bisconimide, p-phenylene bisconimide, 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-bismaleimideethane , 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-dioxane Octane, 1,11-bismaleimide-3,6,9-trioxahedrondecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3 -maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4-diphenylmethane bis(oxadiazole), 2,2-bis[4-(4-oxadiazolephenoxy)phenyl]propane, bis(3,5-dimethyl-4-oxadiazolephenyl)methane, bis(3-ethyl-5-methyl-4-oxadiazolephenyl)methane, bis(3,5-diethyl-4-oxadiazolephenyl)methane, polyphenylmethane maleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used alone or in combination of two or more.

The total content of other maleimide compounds in the resin composition is not particularly limited, but is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the resin solid content in the composition of the present embodiment.

(Cyanate compounds) Cyanate compounds are obtained by reacting phenol resins with cyanogen halides. Specific examples include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 2,2'-bis(4-cyanate phenyl) propane, bis(4-cyanate phenyl) methane, bis(3,5-dimethyl-4-cyanate phenyl) methane, 2,2'-bis(3, 5-dimethyl-4-cyanate phenyl) propane, 2,2'-bis(4-cyanate phenyl) ethane, 2,2'-bis(4-cyanate phenyl) hexafluoropropane, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) sulfide, phenol novolac cyanate, and a phenol-dicyclopentadiene copolymer obtained by converting the hydroxyl group to a cyanate group, etc., but not limited to these. In addition, the cyanate compound whose synthesis method is described in Japanese Patent Laid-Open No. 2005-264154 is particularly preferred as a cyanate compound because of its low hygroscopicity, flame retardancy, and excellent dielectric properties. In order to trimerize the cyanate group to form a s-triazine ring as needed, the cyanate compound may also contain a catalyst such as zinc cycloalkanoate, cobalt cycloalkanoate, copper cycloalkanoate, lead cycloalkanoate, zinc octanoate, tin octanoate, lead acetylacetonate, dibutyltin maleate, etc. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.0001 to 0.0015 parts by mass, relative to 100 parts by mass of the total mass of the composition.

In the composition, the total content of the cyanate compound is not particularly limited, but is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Phenol resin) As the phenol resin, any generally known phenol resin can be used as long as it has two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin , multifunctional naphthol resins, anthracene-type phenol resins, naphthalene skeleton modified novolac-type phenol resins, phenol aralkyl-type phenol resins, naphthol aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, biphenyl-type phenol resins, alicyclic phenol resins, polyol-type phenol resins, phosphorus-containing phenol resins, phenol resins containing polymerizable unsaturated hydrocarbons, and hydroxyl-containing silicone resins, etc., but there is no particular limitation. These phenol resins can also be used alone or in combination of two or more.

The total content of the phenolic resin in the composition is not particularly limited, but is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Epoxy resin) The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, Epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthalene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanuric acid esters, glycidyl ester type epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, naphthol aralkyl novolac type epoxy resins, aralkyl novolac type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidyl amine, compounds obtained by epoxidizing double bonds of butadiene and the like, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in combination of two or more.

The total content of the epoxy resin in the composition is not particularly limited, but is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Oxycyclobutane resin) As the oxycyclobutane resin, generally known ones can be used. For example, alkyl cyclooxybutanes such as cyclooxybutane, 2-methylcyclooxybutane, 2,2-dimethylcyclooxybutane, 3-methylcyclooxybutane, 3,3-dimethylcyclooxybutane, 3-methyl-3-methoxymethylcyclooxybutane, 3,3-bis(trifluoromethyl)perfluorocyclooxybutane, 2-chloromethylcyclooxybutane, 3,3-bis(chloromethyl)cyclooxybutane, biphenyl-type cyclooxybutane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), and OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) can be cited, but there is no particular limitation. These cyclohexane oxybutane resins can be used alone or in combination of two or more.

The total content of the cyclohexane resin in the composition is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Benzoxazine compound) As the benzoxazine compound, any generally known compound can be used as long as it has two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein type benzoxazine, etc. can be listed, but there is no particular limitation. These benzoxazine compounds can be used alone or in combination of two or more.

In the composition, the total content of the benzoxazine compound is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Carbodiimide compound) The carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group in the molecule, and generally known ones can be used. For example, polycarbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, diphenylcarbodiimide, di-tert-butylcarbodiimide, di-β-naphthylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, Carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.), and Stabaxol (registered trademark: manufactured by LANXESS Deutschland GmbH) can be cited. These carbodiimide compounds can be used alone or in combination of two or more.

In the composition, the total content of the carbodiimide compound is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid component in the composition of the present embodiment.

(Compounds having ethylenically unsaturated groups) The compounds having ethylenically unsaturated groups are not particularly limited as long as they have ethylenically unsaturated groups in one molecule. Specific examples of the compound having an ethylenically unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenyl ethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, divinyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, tri(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate ... Alcohol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxyethylpropane tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts thereof, etc.

In addition, urethane (meth)acrylates having both a (meth)acryl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryl group and an ester bond in the same molecule; epoxy (meth)acrylates derived from epoxy resins and having both a (meth)acryl group; reactive oligomers using these bonds in combination, etc. can also be listed as specific examples of compounds having ethylenically unsaturated groups.

The so-called urethane (meth)acrylates include: reactants of hydroxyl-containing (meth)acrylates and polyisocyanates, and optionally other alcohols. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; glycerol (meth)acrylates such as glycerol mono(meth)acrylate and glycerol di(meth)acrylate; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane hexamethylene diisocyanate, and isocyanurates and biuret reaction products thereof. Urethane (meth)acrylates formed by the reaction of polyisocyanates such as acrylate and polyisocyanate.

The so-called polyester (meth)acrylates include, for example: monofunctional (poly)ester (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and/or propylene oxide-modified (meth)acrylate phthalate, ethylene oxide-modified (meth)acrylate succinate, caprolactone-modified (meth)acrylate tetrahydrofurfuryl ester; di(poly)ester (meth)acrylates such as hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono-, di- or tri-(meth)acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. to 1 mol of trihydroxymethylpropane or glycerol.

In addition, there can be mentioned: mono-, di-, tri- or tetra-(meth)acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. to 1 mol of pentaerythritol, dihydroxymethylpropane, trihydroxymethylpropane or tetrahydroxymethylpropane; mono-(meth)acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. to 1 mol of dipentaerythritol; or mono- or poly-(meth)acrylates of triols, tetraols, pentaols or hexaols of polyols such as poly(meth)acrylates.

Furthermore, the following can be cited: (meth)acrylates of polyester polyols which are the reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol with polyacids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, and 5-sodium sulfonate isophthalate, and their anhydrides; (meth)acrylates of polyester diols modified with diol components, polyacids, their anhydrides, and cyclic lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone, etc., and the like.

The so-called epoxy (meth) acrylates refer to compounds having an epoxy group and a carboxylic acid ester compound of (meth) acrylic acid. Examples thereof include: phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trihydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol type epoxy (meth) acrylate, bisphenol A novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate, and acid anhydride-modified epoxy acrylates thereof.

For example, 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 divinyl benzene; or compounds having a vinyl group such as triallyl isocyanurate, trimethylallyl isocyanurate, and diallyl nadic acid imide are also listed as specific examples of compounds having an ethylenically unsaturated group.

As the compound having an ethylenically unsaturated group, commercially available products can be used, for example, KAYARAD (registered trademark) R-604, KAYARAD (registered trademark) R-684, KAYARAD (registered trademark) HX-220, KAYARAD (registered trademark) HX-620, KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) (KAYARAD) (registered trademark) DPCA-60, KAYARAD (registered trademark) DPEA-12, KAYARAD (registered trademark) PET-30, KAYARAD (registered trademark) ZXR-1801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), (registered trademark) ZXR-1806H (trade name), KAYARAD (registered trademark) ZXR-1810H (trade name), KAYARAD (registered trademark) ZXR-1889H (trade name), KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-8001H, KAYARAD (registered trademark) ZCR-8 002H, KAYARAD (registered trademark) ZAR-2001H, KAYARAD (registered trademark) ZAR-2002H, KAYARAD (registered trademark) UXE-3000, KAYARAD (registered trademark) PCR-1222H, CCR-1171H, KAYARAD (registered trademark) ZFR-1494H, etc. These compounds having ethylenically unsaturated groups can be used alone or in combination of two or more.

In the composition, the total content of the compounds having an ethylenically unsaturated group is not particularly limited, but is preferably 0.01 to 60 parts by mass based on 100 parts by mass of the resin solid content in the composition of the present embodiment.

<Hardening accelerator (F)> The resin composition may be further formulated with a hardening accelerator (F). Examples include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazo-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, benzyldimethylamine; Phosphine, tributylphosphine, trioctylphosphine and other phosphines; organic metal salts such as tin octanoate, zinc octanoate, dibutyltin dimaleate, zinc cycloalkanoate, cobalt cycloalkanoate, tin oleate, etc.; metal chlorides such as zinc chloride, aluminum chloride, tin chloride, etc.; organic peroxides such as di-tert-butyl peroxide and diisopropylbenzene peroxide; azo compounds such as azobis(isobutyronitrile) and azobis(dimethylvaleronitrile); mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.; Lewis acids such as boron trifluoride, etc.; salts such as sodium carbonate or lithium chloride, etc.

Specific examples of the curing accelerator (F) are shown below. As organic peroxide-based polymerization initiators, for example, methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetoacetone peroxide, 1,1-bis(tert-butyl peroxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexyl peroxide)cyclohexane, 1,1-bis(tert-hexyl peroxide)3,3,5-trimethylcyclohexane 1,1-bis(tert-butylperoxide)cyclohexane, 2,2-bis(4,4-di-tert-butylperoxidecyclohexyl)propane, 1,1-bis(tert-butylperoxide)cyclododecane, n-butyl 4,4-bis(tert-butylperoxide)valerate, 2,2-(tert-butylperoxide)butane, 1,1-bis(tert-butylperoxide)-2-methylcyclohexane, tert-butylperoxide Hydrogen, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, α,α'-bis(tert-butyl peroxide)diisopropylbenzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, tributyl) hexyne-3, isobutyl peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, cinnamic acid peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxide 1-Hexyl peroxydicarbonate, 2-butyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl) peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, α,α'-bis(peroxyneodecanyl) diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxytrimethylacetate, tert-butyl peroxytrimethylacetate, 2,5-dimethyl-2,5-bis(peroxy2-ethylhexanoyl)hexane, 1,1,3,3-tetramethylbutyl-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl-2-peroxy Hexanoate, tert-hexyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-isobutyrate, tert-butyl peroxide-maleic acid, tert-butyl peroxide-laurate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide-isopropyl monocarbonate, tert-butyl peroxide-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(peroxybenzoyl)hexane, tert-butyl peroxide-acetate, tert-hexyl peroxide-benzoate, tert-butyl peroxide-m-toluoyl benzoate, tert-butyl peroxide-benzoate, bis(peroxytert-butyl)isophthalate, tert-butyl peroxide-allyl monocarbonate, 3,3',4,4'-tetra(peroxytert-butylcarbonyl)benzophenone, etc.

Examples of azo-based polymerization initiators include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamide) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionamide) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamide] 2,2'-azobis[2-methyl-N-(phenylmethyl)propanamide] dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propanamide] dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropanamide] dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazopyrimidine-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1 ,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile], etc.

Furthermore, as the hardening accelerator (F), for example, phosphine compounds, compounds having phosphonium salts, imidazole compounds, etc. can be listed, and one of them or a combination of two or more thereof can be used. Among them, imidazole compounds are preferred. Imidazole compounds have particularly excellent functions as catalysts, and thus can more effectively promote the polymerization reaction of the dimaleimide resin (A) and the maleimide resin (B).

The imidazole compound is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole. Among them, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferred. By using these compounds, the reaction of the bismaleimide resin (A) and the maleimide resin (B) can be further promoted, and the heat resistance of the obtained cured product can be improved. These compounds can be used alone or in combination of two or more.

The phosphine compound is not particularly limited, and examples thereof include: primary phosphines such as alkyl phosphines such as ethyl phosphine and propyl phosphine, and phenyl phosphine; secondary phosphines such as dialkyl phosphines such as dimethyl phosphine and diethyl phosphine, diphenyl phosphine, methyl phenyl phosphine, and ethyl phenyl phosphine; tertiary phosphines such as trialkyl phosphine such as trimethyl phosphine, triethyl phosphine, tributyl phosphine, and trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, alkyl diphenyl phosphine, dialkyl phenyl phosphine, tribenzyl phosphine, tritolyl phosphine, tri-p-phenylvinyl phosphine, tri(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenyl phosphine, tri-4-methoxyphenyl phosphine, and tri-2-cyanoethyl phosphine. Among them, tertiary phosphines are preferably used. These may be used alone or in combination of two or more.

Examples of the compound having a phosphonium salt include compounds having a tetraphenylphosphonium salt, an alkyltriphenylphosphonium salt, a tetraalkylphosphonium, and the like. More specifically, examples include tetraphenylphosphonium-thiocyanate, tetraphenylphosphonium-tetra-p-methylphenylborate, butyltriphenylphosphonium-thiocyanate, tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid.

The curing accelerator (F) may be used alone or in combination of two or more. The content of the curing accelerator (F) is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the reactive resin component.

The resin composition may contain, for example, an inorganic filler, a release agent, a flame retardant, an ion scavenger, an antioxidant, a bonding agent, a stress reducing agent, a coloring agent, and a coupling agent as components (F) other than essential components within a range that does not impair the effects of the present invention.

(Filler) In order to improve the coating properties or heat resistance and other properties of the curable resin composition of the present invention, a filler may be further included. As a filler, it is preferred that it has insulation and does not block the transmittance relative to the wavelength of 405 nm (h-ray). There is no particular limitation on the filler, and examples thereof include: silica (e.g., natural silica, fused silica, synthetic silica, hollow silica, etc.), aluminum compounds (e.g., alumina, aluminum hydroxide, aluminum oxide, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium Compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., glass staple fibers, spherical glass, glass micropowder (e.g., E glass, T glass, D glass, etc.), silicone powder, fluororesin fillers, urethane resin fillers, (meth) acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers can be used alone or in combination of two or more.

Among these, preferably, at least one of the group consisting of silica, alumina, barium sulfate, silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber is selected. These fillers can also be surface treated with the silane coupling agent described below.

From the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition and obtaining good coating properties, silicon dioxide is preferred, and fused silicon dioxide is more preferred. Specific examples of silicon dioxide include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatechs Co., Ltd.

The particle size of the filler is not particularly limited, but is generally 0.005 μm to 100 μm, preferably 0.01 μm to 50 μm.

In the resin composition, the content of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less, relative to 100 parts by mass of the resin solid component in the resin composition. Furthermore, when the filler is contained, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving the coating properties, heat resistance, etc., it is usually 1 part by mass relative to 100 parts by mass of the resin solid component in the resin composition.

(Silane coupling agent and wetting dispersant) In the resin composition, a silane coupling agent and/or wetting dispersant can be used in combination to improve the dispersibility of the filler and the bonding strength between the polymer and/or resin and the filler. As these silane coupling agents, there is no particular limitation as long as they are silane coupling agents generally used for surface treatment of inorganic materials. Specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and [3-(6-aminohexylamino)propyl]trimethoxysilane. , and aminosilanes such as [3-(N,N-dimethylamino)-propyl]trimethoxysilane; 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-glycidyloxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; epoxysilanes such as vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy Vinyl silanes such as methoxy(7-octen-1-yl)silane and trimethoxy(4-vinylphenyl)silane; methacryl silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; acryl silanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; isocyanate silanes such as tris-(trimethoxysilylpropyl)isocyanurate Cyanurate silane series; 3-butylpropyltrimethoxysilane, 3-butylpropyldimethoxymethylsilane and other butylsilane series; 3-ureidopropyltriethoxysilane and other ureidosilane series; p-phenylphenyltrimethoxysilane and other styrylsilane series; N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride and other cationic silane series; [3-(trimethoxysilyl)propyl]succinic anhydride and other acid anhydride series; phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, p-tolyltrimethoxysilane and other phenylsilane series; trimethoxy (1-naphthyl) silane and other arylsilane series. These silane coupling agents can be used alone or in combination of two or more.

In the resin composition, the content of the silane coupling agent is not particularly limited, and is generally 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solid component in the resin composition. As a wetting dispersant, there is no particular limitation as long as it is a dispersion stabilizer used for coating purposes. As specific examples, for example, wetting dispersants such as DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, W903, etc. manufactured by BYK Chemie Japan Co., Ltd. can be cited. These wetting dispersants can be used alone or in combination of two or more. In the resin composition, the content of the wetting dispersant is not particularly limited, and is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solid component in the resin composition.

<Organic solvent (G)> The resin composition may contain an organic solvent as needed. If an organic solvent is used, the viscosity of the resin composition can be adjusted. There is no particular limitation on the type of organic solvent as long as it can dissolve a part or all of the resin in the resin composition. Examples of such organic solvents include: halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; Solvents; 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 hydroxy isobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene, etc.

Among these, cyclopentanone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred because they can show excellent solubility in other resins and compounds such as the dimaleimide compound (A) and the maleimide compound (B), and further, the photopolymerization initiator (C) and the compound containing one or more carboxyl groups (D), and can easily prepare a varnish having good solubility. These organic solvents can be used alone or in combination of two or more.

[Manufacturing method of resin composition] The resin composition is prepared by appropriately mixing a dimaleimide compound (A), a maleimide compound (B), a photocuring initiator (C), and a compound containing one or more carboxyl groups (D) as required, a filler, other resins, other compounds, and additives. The resin composition can be suitably used as a varnish when preparing a resin sheet of the present embodiment described later. In addition, the organic solvent used in the preparation of the varnish is not particularly limited, and its specific example is as described above.

The method for producing the resin composition includes, for example, mixing the above-mentioned components into a solvent in sequence and stirring them thoroughly. The resin composition has excellent light curing properties, and the cured product obtained from the resin composition has excellent heat resistance, thermal stability, and insulation reliability.

When manufacturing the resin composition, known treatments (stirring, mixing, kneading treatments, etc.) for uniformly dissolving or dispersing the components may be performed as necessary. Specifically, by performing a stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity, the dispersibility of the components in the resin composition can be improved. Stirring, mixing, and kneading treatments may be appropriately performed using known devices such as stirring devices for the purpose of dispersion, such as ultrasonic homogenizers, devices for the purpose of mixing, such as three-rollers, ball mills, bead mills, sand mills, and mixing devices of a revolving or rotating type. In addition, an organic solvent may be used as necessary when preparing the resin composition. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

The resin composition can be suitably used as a varnish when preparing 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 of an organic solvent to 100 parts by mass of the components other than the organic solvent in the resin composition of the present embodiment, and performing the known mixing treatment (stirring, kneading treatment, etc.).

[Applications] The resin composition can be preferably used for applications of resin compositions that require insulation reliability. For example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die attach materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Among these, the resin composition is excellent in light curing, heat resistance, and thermal stability, so it can be suitably used as an insulating layer of a multilayer printed wiring board or a solder resist.

[Hardened product] The cured product is obtained by curing the resin composition. The cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light. Regarding the wavelength range of the light, it is preferred to cure within the range of 100 nm to 500 nm where curing is efficiently performed by a photopolymerization initiator, etc.

[Resin sheet] 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, wherein the resin layer contains a resin composition. The resin sheet can be manufactured by applying the resin composition on the support and drying it. The resin layer in the resin sheet has excellent heat resistance, thermal stability, and insulation reliability.

The support body may be a known one, but preferably a resin film. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetate film. Among these, PET film is preferred.

In order to facilitate peeling from the resin layer, the resin film is preferably coated with a peeling agent on the surface. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support tends to be easily broken when the support is peeled off before development, and if the thickness exceeds 100 μm, the resolution tends to decrease when exposing from the support.

In order to reduce light scattering during exposure, the resin film is preferably a film with excellent transparency.

Furthermore, in the resin sheet, the resin layer can also be protected by a protective film. By protecting the side of the resin layer with a protective film, dust or the like can be prevented from being attached to the surface of the resin layer or from being 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 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. When the thickness is less than 1 μm, the operability of the protective film tends to be reduced, and if it exceeds 50 μm, the cost performance tends to be poor. Furthermore, the protective film is preferably such that the adhesion between the resin layer and the protective film is smaller than the adhesion between the resin layer and the support.

The method for manufacturing the resin sheet can be exemplified by the following method: the resin composition of the present embodiment is applied to a support such as a PET film, and the organic solvent is removed by drying to manufacture the resin sheet. Regarding the coating method, for example, it can be carried out by a known method using a roller coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a blade coater, and an extrusion coater. Drying can be carried out, for example, by heating in a dryer at 60°C to 200°C for 1 minute to 60 minutes.

The amount of the organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer from the viewpoint of preventing the organic solvent from diffusing in the subsequent steps. From the viewpoint of improving the workability, the thickness of the resin layer is preferably 1 μm to 50 μm.

The resin sheet can be preferably used for manufacturing the insulating layer of a multi-layer printed wiring board.

[Multi-layer printed wiring board] The multi-layer printed wiring board of the present embodiment has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition. For example, the insulating layer can be obtained by stacking and curing more than one resin sheet. There is no particular limitation on the number of layers of the insulating layer and the conductive layer, and the number of layers can be appropriately set according to the target use. In addition, there is no particular limitation on the order of the insulating layer and the conductive layer. As the conductive layer, it can be a metal foil used for various printed wiring board materials, for example, metal foils such as copper and aluminum can be listed. Examples of copper metal foils include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is usually 1 μm to 100 μm. Specifically, it can be produced by the following method.

(Lamination step) In the lamination step, a vacuum lamination press is used to press the resin layer side of the resin sheet onto one or both sides of the circuit substrate. Examples of circuit substrates include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, bismaleimide triazine (BT) resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the so-called circuit substrate refers to a substrate having a patterned conductive layer (circuit) formed on one or both sides of the substrate. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit substrate. Furthermore, the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by laminating and curing one or more resin sheets of the present embodiment, or may be an insulating layer obtained by laminating one or more resin sheets of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. Furthermore, there is no particular limitation on the method of overlapping the resin sheet of the present embodiment with a known resin sheet different from the resin sheet of the present embodiment. The surface of the conductor layer may also be roughened in advance by blackening and/or copper etching. In the lamination step, if the resin sheet has a protective film, the resin sheet and the circuit substrate are preheated as needed after the protective film is peeled off and removed, and the resin layer of the resin sheet is pressed and connected to the circuit substrate while being pressurized and heated. In the present embodiment, a method of pressing the resin layers of the resin sheet to the circuit substrate under reduced pressure by vacuum lamination can be appropriately used.

Regarding the conditions of the lamination step, for example, it is preferred to set the pressing temperature (lamination temperature) to 50°C to 140°C, set the pressing pressure to 1 kgf/ ^cm2 to 15 kgf/ ^cm2 , set the pressing time to 5 seconds to 300 seconds, and perform the lamination under reduced pressure with the air pressure set to 20 mmHg or less. In addition, the lamination step may be a batch type or a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum lamination press. As a commercially available vacuum lamination press, for example, a 2-stage build-up laminator (trade name) manufactured by Nikko Materials (Co., Ltd.) can be listed.

(Exposure step) In the exposure step, after the resin layer is provided on the circuit substrate by the lamination step, the resin layer is irradiated with active energy rays as a light source to harden the resin layer in the irradiated part. The irradiation may be performed via a mask pattern or by a direct drawing method of 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 nm to 600 nm. When ultraviolet rays are used, the irradiation amount is approximately 10 mJ/cm ² to 1000 mJ/cm ² . In addition, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a stepper exposure method, it is preferable to use an active energy ray including a wavelength of 365 nm (i-ray), for example. When using an active energy ray including a wavelength of 365 nm (i-ray), the irradiation amount is approximately 10 mJ/cm ² to 10,000 mJ/cm ² . When a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, it is preferable to use an active energy ray including a wavelength of 405 nm (h-ray), for example. When using an active energy ray including a wavelength of 405 nm (h-ray), the irradiation amount is approximately 10 mJ/cm ² to 10,000 mJ/cm ² . There are two methods of exposure through a mask pattern: a contact exposure method in which the mask pattern is brought into close contact with the multi-layer printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light without close contact. Either method may be used. In addition, when a support is present on the resin layer, exposure may be carried out from the support, or exposure may be carried out after the support is peeled off.

(Development step) In this embodiment, a development step may be included as needed. That is, when there is no support on the resin layer, after the exposure step, the uncured portion (unexposed portion) is removed by wet development and developed, thereby forming a pattern of the insulating layer. In addition, when there is a support on the resin layer, after the exposure step, the uncured portion (unexposed portion) is removed by wet development after the support is removed and developed, thereby forming a pattern of the insulating layer.

In the case of wet development, the developer is not particularly limited as long as it is a developer that selectively dissolves the unexposed portion. For example, organic solvents such as cyclohexanone, cyclopentanone, and γ-butyrolactone; alkaline developers such as tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution can be used. These developers can also be used alone or in combination of two or more.

In addition, as a developing method, for example, it can be carried out by a known method such as immersion, coating, spraying, shaking immersion, brushing, scraping, etc. In pattern formation, these developing methods can also be used in combination as needed. In addition, as a developing method, when a high-pressure spray is used, the resolution is further improved, so it is suitable. When the spray method is used, the spray pressure is preferably 0.02 MPa to 0.5 MPa.

(Post-baking step) After the exposure step or the development step, a post-baking step is performed to form an insulating layer (hardened material). As the post-baking step, there can be cited a step of ultraviolet irradiation using a high-pressure mercury lamp, a step of heating using a clean oven, etc., and these steps can also be used in combination. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, the irradiation amount can be about 50 mJ/ ^cm2 to 10,000 mJ/ ^cm2 . The heating conditions can be appropriately selected as needed, but are preferably in the range of 150° C. to 300° C. and 20 minutes to 180 minutes, and more preferably in the range of 200° C. to 300° C. and 30 minutes to 60 minutes.

(Conductor layer formation step) After forming the insulating layer (hardened material), a conductor layer is formed on the surface of the insulating layer by dry plating. As dry plating, known methods such as evaporation, sputtering, and ion plating can be used. Evaporation (vacuum evaporation) is, for example, a method of placing a multi-layer printed wiring board in a vacuum container and heating the metal to evaporate, thereby forming a metal film on the insulating layer. Sputtering is, for example, a method of placing a multi-layer printed wiring board in a vacuum container, introducing an inert gas such as argon, and applying a DC voltage to cause the ionized inert gas to collide with the target metal, and using the knocked-out metal to form a metal film on the insulating layer.

Then, a conductive layer is formed by electroless plating or electrolytic plating, etc. As a method for subsequent patterning, for example, a subtractive method, a semi-additive method, etc. can be used.

[Sealing material] The sealing material of the present embodiment includes the resin composition of the present embodiment. As a method for producing the sealing material, generally known methods can be appropriately applied without particular limitation. For example, the sealing material can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used in sealing material applications using a known mixer. Furthermore, during mixing, the method for adding the maleimide compound, various additives, and solvents of the present embodiment can appropriately apply generally known methods without particular limitation.

[Fiber-reinforced composite material] The fiber-reinforced composite material of the present embodiment includes the resin composition of the present embodiment and reinforcing fibers. As the reinforcing fibers, generally known ones can be used without particular limitation. For example, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass; carbon fibers; polyarylamide fibers; boron fibers; poly-p-phenylene benzobisoxazole (PBO) fibers; high-strength polyethylene fibers; alumina fibers; and silicon carbide fibers. There is no particular limitation on the shape and arrangement of the reinforcing fibers, and they can be appropriately selected from woven fabrics, nonwoven fabrics, felt, knitted fabrics, ribbons, unidirectional strands, coarse yarns, and chopped materials. In addition, as the shape of the reinforcing fibers, preforms (those in which fabric base fabrics containing reinforcing fibers are layered or sewn together with sewing threads, or fiber structures such as three-dimensional fabrics or woven fabrics) can also be used.

As a manufacturing method for these fiber-reinforced composite materials, generally known methods can be appropriately applied without particular limitation. For example, liquid composite molding, resin film infusion, filament winding, hand lay-up, and pultrusion methods can be listed. Among these, resin transfer molding, which is one of the liquid composite molding methods, can pre-place raw materials other than preforms such as metal plates, foam cores, and honeycomb cores in a molding mold, so it can cope with various uses, and can therefore be preferably used in the case of mass production of composite materials with relatively complex shapes in a short time.

[Adhesive] The adhesive of the present embodiment includes the resin composition of the present embodiment. As a method for producing the adhesive, generally known methods can be appropriately applied without particular limitation. For example, the adhesive can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used in adhesive applications using a known mixer. Furthermore, during mixing, the method for adding the maleimide compound, various additives, and solvents of the present embodiment can appropriately apply generally known methods without particular limitation.

[Semiconductor device] The heat-resistant resin film formed by the resin composition of the present invention can be used in electronic parts such as semiconductor devices or multilayer wiring boards, and organic electroluminescence (EL) display devices. Specifically, it is suitably used for passivation films of semiconductors, surface protection films of semiconductor elements, interlayer insulation films, insulation films of redistribution layers, interlayer insulation films of multilayer wiring for high-density mounting, interlayer insulation films of electronic parts such as inductors or surface acoustic wave (SAW) filters, and insulation films or planarization layers of organic electroluminescent elements, but is not limited to these and various structures can be adopted.

The compounds and compositions of the present invention can also be used in the form of dry film anti-etching agents. That is, the compounds and compositions of the present invention are coated on a base film using a roll coater, a die coater, a doctor blade coater, a rod coater, a gravure coater, etc., and then dried in a drying oven set at 45°C to 140°C, and a prescribed amount of solvent is removed, or a covering film is layered as needed, thereby making a dry film anti-etching agent. At this time, the thickness of the anti-etching agent on the base film is adjusted to 2 μm to 200 μm. As the base film and the covering film, for example, a film of polyester, polypropylene, polyethylene, triacetyl cellulose (TAC), polyimide, etc. is used. Among these films, films treated with a silicone-based release agent or a non-silicone-based release agent may be used as needed. If supplied as a dry film anti-etching agent, the steps of coating and drying on a support can be omitted, and the photosensitive resin composition of the present invention can be used more simply. [Example]

The present invention is described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, the "parts" and "%" in the examples are based on mass. In addition, the compatibility and dielectric properties, heat resistance (glass transition temperature (Tg)), thermal stability (5% weight reduction temperature (Td5)), and crack resistance after photopatterning in each example and comparative example were evaluated in the following manner. The molecular weight measurement conditions are as follows. Model: GPC TOSOH HLC-8220GPC Column: Super HZM-N Solvent: tetrahydrofuran (THF); 0.35 ml/min, 40°C Detector: differential refractometer (refractive index, RI) Molecular weight standard: polystyrene

<Bismaleimide compound (A)> Synthesis Example 1 (A-1) In a 1 L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirring apparatus, 165 g of toluene and 165 g of N-methylpyrrolidone were placed. Then, 26.6 g (0.20 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 11.7 g (0.02 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9 g (0.22 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture. The mixture was heated and refluxed for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water generated. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials, and a varnish of a bismaleimide compound was obtained. Thereafter, the varnish was added dropwise to 1,000 g of methanol to perform a reprecipitation step, remove the solvent and dry it, thereby obtaining 72 g (yield 72%, Mw=4,000) of the target light brown solid bismaleimide compound (A-1).

Synthesis Example 2 (A-2) In a 1 L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirring apparatus, 165 g of toluene and 165 g of N-methylpyrrolidone were placed. Then, 26.6 g (0.20 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 23.4 g (0.04 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9 g (0.22 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture. The mixture was heated and refluxed for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water generated. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials, and a varnish of a bismaleimide compound was obtained. Thereafter, the varnish was added dropwise to 1,000 g of methanol to perform a reprecipitation step, remove the solvent and dry it, thereby obtaining 72 g (yield 72%, Mw=4,100) of the target light brown solid bismaleimide compound (A-2).

Synthesis Example 3 (A-3) In a 1 L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark device, powder inlet, nitrogen inlet and stirring device, 165 g of toluene and 165 g of N-methylpyrrolidone were added. Then, 26.6 g (0.20 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 35.1 g (0.06 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9 g (0.22 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture. The mixture was heated and refluxed for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water generated. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials, and a varnish of a bismaleimide compound was obtained. Thereafter, the varnish was added dropwise to 1,000 g of methanol to perform a reprecipitation step, remove the solvent and dry it, thereby obtaining 72 g (yield 72%, Mw=3,700) of the target light brown solid bismaleimide compound (A-3).

<Maleimide compound (B)> As maleimide compound (B), the following four compounds were prepared. (B-1) Maleimide compound Made by Nippon Kayaku Co., Ltd., trade name "MIR-3000" (B-2) Maleimide compound Made by Nippon Kayaku Co., Ltd., trade name "MIR-5000" (B-3) Maleimide compound Made by KI Chemical, trade name "BMI-70" (B-4) Maleimide compound Made by Yamato Chemical Industries, Ltd., trade name "BMI-2300"

<Photopolymerization initiator (C)> Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE-02")

(Example 1 to Example 10 and Comparative Example 1 to Comparative Example 4) The components (A) to (C) in the amounts (parts by mass) shown in Table 1 and Table 2 and 103 parts by mass of cyclopentanone as an organic solvent (G) were prepared to prepare the photosensitive resin compositions of Example 1 to Example 10 and Comparative Example 1 to Comparative Example 4.

<Evaluation of properties> The following properties were measured for the prepared curable resin composition and cured film. The results are shown in Tables 1 and 2.

[Compatibility] Visual compatibility refers to the state of the curable resin composition after mixing and stirring components (A) to (G). Good compatibility means that there is no precipitate and it can be applied to the base material, while poor compatibility means that there is precipitate and it is difficult to apply to the base material. (Evaluation criteria) ○: No precipitate ×: Precipitate

[Photopatterning evaluation] The photosensitive resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were spin-coated on a silicon substrate and heated at 100°C for 2 minutes to form a coating with a thickness of 10 μm to 15 μm. Subsequently, a "Ultra-High-Pressure Mercury Lamp 500 W MultiLight" manufactured by USHIO was used, and a step exposure meter No. 2 step exposure meter manufactured by Kodak was used to perform reduced projection exposure with i-rays (365 nm). The exposure amount was 2000 mJ/cm ² . After exposure, the film was heated at 150°C for 15 minutes and developed using propylene glycol monomethyl ether glycol. For the crack resistance, the pattern after development was observed under a microscope to determine whether cracks occurred on the pattern. (Crack resistance determination criteria) ○: No cracks ×: Cracks In addition, for the hardening property, it was determined whether the pattern remained after development. (Photohardening determination criteria) ○: After development, the pattern remained ×: After development, no pattern remained The results of crack resistance and photohardening are shown in Table 1.

[Dielectric properties] First, the photosensitive resin composition obtained in each embodiment and comparative example was applied onto a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metal Co., Ltd.) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the film-like photosensitive resin composition after drying was 20 μm. The film-like photosensitive resin composition was exposed to 3000 mJ/ ^cm2 using a light source (Ultra-High-Pressure Mercury Lamp 500 W MultiLight (trade name) manufactured by USHIO) that can irradiate active energy rays including a wavelength of 405 nm (h-rays), and then cured by heating at 250°C for 60 minutes in a nitrogen atmosphere. The copper foil was then removed by etching to obtain a cured film. The cured resin film was cut into 80 mm × 3 mm test pieces. The obtained test piece was placed in an environment of 25°C and 20% for one day, and then the relative dielectric constant and dielectric loss tangent at 10 GHz were measured using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.). The measuring instrument used was a vector network analyzer ADMSO10c1 manufactured by AET Co., Ltd., and the cavity resonator used was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd. The results are shown in Table 1.

[Evaluation of glass transition temperature (Tg)] The photosensitive resin composition obtained in each embodiment and comparative example was applied onto a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metal Co., Ltd.) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the film-like photosensitive resin composition after drying became 20 μm. The film-like photosensitive resin composition was exposed to an exposure dose of 3000 mJ/ ^cm2 using a light source (Ultra-High-Pressure Mercury Lamp 500 W MultiLight (trade name) manufactured by USHIO) capable of irradiating active energy rays including a wavelength of 405 nm (h-rays), and then cured by heating at 250°C for 60 minutes in a nitrogen atmosphere. The copper foil was then removed by etching to obtain a cured film. The dynamic viscoelasticity of the cured product of the dimaleimide prepared as described above was measured using a dynamic viscoelasticity measuring device (DMA) (RSA-G2 manufactured by TA Instruments) (frequency 1 Hz, tensile mode, heating rate 5°C/min), and the glass transition temperature was obtained from the maximum value of the loss tangent (tanδ). Furthermore, from the perspective of compatibility, the tanδ peak waveform was verified and the number of peaks was counted. The results are shown in Table 1.

[Resistance to thermal decomposition] The photosensitive resin composition obtained in each of the Examples and Comparative Examples was applied onto a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metal Co., Ltd.) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the film-like photosensitive resin composition after drying was 20 μm. The film-like photosensitive resin composition was exposed to an exposure dose of 3000 mJ/ ^cm2 using a light source (Ultra-high-pressure mercury lamp 500 W MultiLight (trade name) manufactured by USHIO) that can irradiate active energy rays including a wavelength of 405 nm (h-rays), and then cured by heating at 250°C for 60 minutes in a nitrogen atmosphere. The copper foil was then removed by etching to obtain a cured film. The cured product was cut into 4 mm squares, and 1.0 mg to 5.0 mg were weighed on a measuring pan. The 5% weight loss rate (Td5) was measured under the conditions of an air flow rate of 100 mL/sec and a temperature increase rate of 10°C/min. A thermogravimetric analysis/differential scanning calorimeter (TGA/DSC) 1 (manufactured by METTLER TOLEDO) was used as the measurement device.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 A-1 60 A-2 80 A-3 80 70 60 50 60 60 80 60 B-1 B-2 B-3 B-4 C 3 3 3 3 3 3 3 3 3 3 G 103 103 103 103 103 103 103 103 103 103 compatibility ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Light hardening ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Anti-tear ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance (℃) 215 228 242 272 239 239 218 236 228 251 Dielectric constant (Dk) 2.72 2.63 2.73 2.64 2.69 2.85 2.66 2.95 2.79 2.77 Dielectric loss tangent (Df) 0.0033 0.0036 0.0038 0.0039 0.0047 0.0042 0.0036 0.0051 0.0042 0.0054 Td5 (℃) 382 391 395 400 388 405 383 387 383 396

[Table 2] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 A-1 A-2 A-3 B-1 100 B-2 100 B-3 100 B-4 100 C 3 3 3 3 G 103 103 103 103 compatibility ○ ○ ○ ○ Light hardening × × × × Anti-tear -* -* -* -* Heat resistance (℃) -* -* -* -* Dielectric constant (Dk) -* -* -* -* Dielectric loss tangent (Df) -* -* -* -* Td5 (℃) -* -* -* -* *: The light curing property is low and a hardened film cannot be produced, so it cannot be evaluated.

As clearly shown in the results shown in Table 1, by using the photosensitive resin composition of the present invention, an excellent hardened material with good compatibility, light curing, and crack resistance, low dielectric properties, a high glass transition temperature of more than 200°C, and high thermal decomposition resistance of more than 380°C can be obtained. [Industrial Applicability]

As described above, the present invention can form fine patterns with relatively low exposure (2000 mJ/ ^cm2 or less), and can obtain a resin sheet having a high glass transition temperature (Tg) of 200°C or more, high thermal decomposition resistance of 380°C or more, a good dielectric loss tangent of 0.006 or less, and good crack resistance. Therefore, the bismaleimide compound and photosensitive resin composition of the present invention are very useful as surface protective films, interlayer insulating films, and insulating films of redistribution layers of semiconductor devices.

without

Claims (7)

A resin composition comprises: a bismaleimide compound (A) having a cyclic imide bond, which is obtained by reacting an aromatic diamine (a-1) represented by the following formula (1), a tetrabasic acid dianhydride (a-3) and maleic anhydride; and a maleimide compound (B), which is at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), and a compound represented by the following formula (8); ( _R1 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); (In formula (2), R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent; n represents an integer of 1 to 10); (In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group; n represents an integer from 1 to 10); (In formula (4), R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent); (In formula (5), _R9 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and _R10 each independently represents a hydrogen atom or a methyl group); (In formula (6), R ₁₁ each independently represents a hydrogen atom, a methyl group, or an ethyl group); (In formula (7), R ₁₂ each independently represents a hydrogen atom or a methyl group; n represents an integer from 1 to 10); (In formula (8), a plurality of R ₁₃ 's each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m represents an integer of 0 to 3; n is a repeating number, and its average value is 1<n<5). A resin composition comprising: a bismaleimide compound (A) represented by the following formula (9); and a maleimide compound (B) selected from the group consisting of a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), a compound represented by the formula (5), a compound represented by the formula (6), a compound represented by the formula (7), and a compound represented by the formula (8); (In formula (9), R ₁₆ independently represents a tetravalent organic group including a cyclic structure; R ₁₅ independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; R ₁₄ independently represents the following formula (10); R ₁₇ is R ₁₄ or R ₁₆ ; m is 1 to 100, and n is 0 to 100; in addition, the order of each repeating unit enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random; (R ₁₈ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4)). The resin composition as claimed in claim 1, wherein the tetrabasic acid dianhydride (a-3) comprises the bismaleimide compound (A) selected from the group consisting of the following formula (11) to formula (19); (In formula (14), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (20)); . The resin composition as described in any one of claims 1 to 3 further comprises a photocuring initiator (C). A hardened material comprising the resin composition as described in any one of claims 1 to 3. A semiconductor element comprising a surface protection film, an interlayer insulating film, or an insulating film of a redistribution layer comprising the resin composition as described in any one of claims 1 to 3. A dry film anticorrosive is obtained by sandwiching the resin composition as described in any one of claims 1 to 3 between a substrate and the substrate.