Resin composition, cured product, semiconductor element and dry film resist

Abstract

The purpose of the present invention is to provide a resin composition containing a bismaleimide compound, which can be patterned by light, has a glass transition temperature of 200 DEG C or higher, and has a low dielectric loss tangent. A resin composition containing: a bismaleimide compound (A) having a cyclic imide bond, which is obtained by reacting an aromatic diamine (a-1) represented by formula (1), a tetrabasic acid dianhydride (a-3), and maleic anhydride; and a maleimide compound (B) other than the bismaleimide compound (A). # imgabs0 #

Description

Technical Field

[0001] The invention relates to a resin composition containing a bismaleimide compound. Background Art

[0002] In recent years, electronic devices have been miniaturized and have become more advanced, and in multilayer 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 there is a demand for the development of insulating materials with excellent dielectric properties.

[0003] In the past, polyimide resins, polybenzoxazole resins, etc. with excellent heat resistance or mechanical properties were widely used in surface protection films or interlayer insulating films of semiconductor elements (Patent Document 1). In the case where polyimide resins or polybenzoxazole resins are used as surface protection films or interlayer insulating films, it is known that there is a method of forming through holes by etching methods using positive photoresists containing these resins. However, the problem in the method is that complicated processes such as coating or stripping of photoresists are required. Therefore, for the purpose of rationalizing the operation process, heat-resistant materials with photosensitivity have been studied (Patent Document 2).

[0004] It is known that among these materials, the dielectric properties are not satisfactory for high-frequency band applications represented by the keyword 5G (5th Generation Mobile Communication Technology). 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 the above materials, lower dielectric properties are required for high-frequency applications.

[0005] On the other hand, Patent Document 4 reports that a resin film made of a resin composition as a non-epoxy material, which contains a bismaleimide resin having a long-chain alkyl group and a curing agent, has excellent low dielectric properties.

[0006] Furthermore, Patent Documents 5 and 6 disclose polyimides 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.

[0007] Patent Document 7 discloses a bismaleimide resin having both a long-chain aliphatic chain portion and an alicyclic structure portion, exhibiting a low dielectric loss tangent, and having a glass transition point (Tg) of 100° C. or higher.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Laid-Open No. 11-199557

[0011] Patent Document 2: Japanese Patent Laid-Open No. 11-24271

[0012] Patent Document 3: Japanese Patent Application Publication No. 2011-132507

[0013] Patent Document 4: International Publication No. 2016 / 114287

[0014] Patent Document 5: Japanese Patent Application Publication No. 2017-119361

[0015] Patent Document 6: Japanese Patent Application Publication No. 2019-104843

[0016] Patent Document 7: Japanese Patent Application Publication No. 2021-123672 Summary of the invention

[0017] Problems to be solved by the invention

[0018] In recent years, it is known that although low molecular weight aromatic maleimide achieves 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 is low. In addition, it is also known that bismaleimide resins with long-chain alkyl groups have high mobility of the reaction site, good photoreactivity, and low dielectric loss tangent due to their long-chain alkyl groups, but low Tg.

[0019] Regarding the bismaleimide compound having both long-chain alkyl and alicyclic structural parts described in Patent Document 7, if the ratio of the long-chain alkyl group becomes high, it becomes very difficult to achieve a high Tg of more than 200°C, and if the ratio of the alicyclic structural parts becomes high, 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 a maleimide resin alone.

[0020] The film described in Patent Document 4 is essentially a combination of a bismaleimide resin having a long-chain alkyl group and a hard low-molecular aromatic maleimide, but has poor compatibility, is prone to uneven properties or curing, and is very difficult to achieve a high glass transition temperature (Tg) of more than 200°C required for semiconductor element use. In addition, the polyimide described in Patent Documents 5 and 6 is difficult to use when cured alone and has poor compatibility with other resins. In addition, polyimide undergoes closed-loop dehydration during curing, so when, for example, a redistribution layer is stacked, gaps may be generated and planarization may not be possible depending on the conditions of use.

[0021] Therefore, an object of the present invention is to provide a resin composition containing a bismaleimide compound which can be patterned by light, has a glass transition temperature of 200° C. or higher, and has a low dielectric loss tangent.

[0022] Technical means of solving problems

[0023] The present inventors have conducted extensive studies to solve the above problems and have found that the following resin composition containing a bismaleimide compound can achieve the above objects, thereby completing the present invention.

[0024] That is, the present invention relates to the following [1] to [7]. [1]

[0026] 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).

[0027] [Chemistry 1]

[0028]

[0029] (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)

[0030] [Chemistry 2]

[0031]

[0032] (In formula (2), R2, R3, and R4 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)

[0033] [Chemistry 3]

[0034]

[0035] (In formula (3), R5 each independently represents a hydrogen atom or a methyl group; n represents an integer of 1 to 10)

[0036] [Chemistry 4]

[0037]

[0038] (In formula (4), R6, R7, and R8 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent)

[0039] [Chemistry 5]

[0040]

[0041] (In formula (5), R9 each independently represents a hydrogen atom, a methyl group, or an ethyl group, R 10 each independently represents a hydrogen atom or a methyl group)

[0042] [Chemistry 6]

[0043]

[0044] (In formula (6), R 11 each independently represents a hydrogen atom, a methyl group, or an ethyl group)

[0045] [Chemistry 7]

[0046]

[0047] (In formula (7), R 12 Each independently represents a hydrogen atom or a methyl group; n4 represents an integer from 1 to 10)

[0048] [Chemistry 8]

[0049]

[0050] (In formula (8), there are multiple R 13 Each independently represents a hydrogen atom, 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) [2]

[0052] A resin composition comprising: a bismaleimide compound (A) represented by the following formula (9); and a maleimide compound (B), selected from at least one of 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).

[0053] [Chemistry 9]

[0054]

[0055] (In formula (9), R 16 independently represent a tetravalent organic group containing a cyclic structure; R 15 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 14 are independently represented by the following formula (10); R 17 For R 14 or R 16 ; m is 1 to 100, n is 0 to 100; in addition, the order of the repeating units enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random;

[0056] [Chemistry 10]

[0057]

[0058] (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) [3]

[0060] The resin composition according to technical solution 1 includes the bismaleimide compound (A) in which the tetrabasic acid dianhydride (a-3) includes a compound selected from the group consisting of the following formula (11) to formula (19).

[0061] [Chemistry 11]

[0062]

[0063] (In formula (14), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (20))

[0064] [Chemistry 12]

[0065] [4]

[0067] The resin composition according to any one of Technical Solutions 1 to 3 further comprises a photocuring initiator (C). [5]

[0069] A hardened material comprising the resin composition according to any one of technical solutions 1 to 4. [6]

[0071] A semiconductor element comprises a surface protection film, an interlayer insulating film, or an insulating film for a redistribution layer comprising the resin composition containing a bismaleimide compound according to any one of technical solutions 1 to 4. [7]

[0073] A dry film resist is obtained by sandwiching a resin composition containing a bismaleimide compound according to any one of technical solutions 1 to 4 by a substrate.

[0074] Effects of the Invention

[0075] The present invention provides a resin composition having good photocurability, a high glass transition temperature (Tg) of 200°C or above, a good dielectric loss tangent, a resin sheet using the resin composition, a multilayer printed wiring board and a semiconductor device, wherein the resin composition has good photocurability, a high glass transition temperature (Tg) of 200°C or above, and a good dielectric loss tangent, and a good resin sheet can be obtained. DETAILED DESCRIPTION

[0076] Hereinafter, the present invention will be described in detail.

[0077] The present invention is a resin composition comprising a bismaleimide compound (A) and a maleimide compound (B).

[0078] <Bismaleimide compound (A)>

[0079] 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) and a tetrabasic acid dianhydride (a-3) represented by the following formula (1). This 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 be reacted.

[0080] [Chemistry 13]

[0081]

[0082] (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)

[0083] The bismaleimide compound (I) is a bismaleimide compound represented by the following general formula (2).

[0084] [Chemistry 14]

[0085]

[0086] (In formula (2), R 16 independently represent a tetravalent organic group containing a cyclic structure; R 15 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 14are independently represented by the following formula (10); R 17 For R 14 or R 15 ; n is 1 to 100, m is 0 to 100; in addition, the order of the repeating units enclosed by n and m is not limited, and the bonding pattern may be alternating, block, or random;

[0087] [Chemistry 15]

[0088]

[0089] (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)

[0090] In the above formula (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.

[0091] 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. Of 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 chips and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins.

[0092] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0093] 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.

[0094] As R1, in addition to showing excellent adhesion to chips and substrates, etc., it also shows 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 a hydrogen atom, a methyl group, and a hydroxyl group, and even more preferably a hydrogen atom.

[0095] In the formula (1), each l independently represents an integer of 1 to 4. As l, in order to exhibit excellent adhesion to chips and substrates, etc., as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, it is preferred that all R1s are hydrogen atoms, and thus 4 is preferred.

[0096] 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.

[0097] [Chemistry 16]

[0098]

[0099] [Chemistry 17]

[0100]

[0101] [Chemistry 18]

[0102]

[0103] The bismaleimide compound (A) is not particularly limited as long as it exerts 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 the present 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.

[0104] Generally, the light transmittance of maleimide compounds is poor. Therefore, if the resin composition described later contains maleimide compounds, light will not fully reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator is difficult to generate free radicals. Therefore, in general, the photoradical reaction of maleimide compounds is difficult to proceed, and even if the free radical polymerization or dimerization reaction of the maleimide monomer is carried out, its reactivity is very low. However, the bismaleimide compound (A) has excellent light transmittance because the maleimide group is bonded to the aromatic ring via a methylene group and the conjugation length is short. Therefore, light fully reaches the photocuring initiator, thereby efficiently causing the photoradical reaction of maleimide. In addition, when a chloroform solution containing the maleimide compound at 1% by mass is prepared and the light transmittance of the chloroform solution is measured using light with a wavelength of 405nm (h-ray), the transmittance is more than 3%, showing very excellent light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct writing exposure method, a photoradical reaction of maleimide is efficiently induced even when active energy rays including a wavelength of 405 nm (h-rays) are used.

[0105] When using active energy rays including a wavelength of 405 nm (h-rays), if the photocuring initiator does not absorb the light of the wavelength of 405 nm (h-rays) and generate free radicals, polymerization will not proceed. Therefore, in such a case, as the photocuring initiator described later, it is preferable to use a photocuring initiator whose absorbance at a wavelength of 405 nm (h-rays) is 0.1 or more and shows very excellent absorption to light of a wavelength of 405 nm (h-rays).

[0106] 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 can fully reach the photocuring initiator, and free radicals generated by the photocuring initiator can be used to carry out a free radical reaction, so that photocuring can be carried out in a resin composition containing a large amount of maleimide compound.

[0107] Furthermore, since the cured product containing the resin composition of the present embodiment is excellent in light curing property, heat resistance, and thermal stability, a protective film and an insulating layer can be suitably formed.

[0108] In addition, the bismaleimide compound (A) may also 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, 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, and more preferably 10 to 50 carbon atoms. As the branched divalent hydrocarbon group, it may be any of a saturated aliphatic hydrocarbon group and an unsaturated hydrocarbon group, and it may also have an alicyclic structure or an aromatic ring structure in the middle of the molecular chain. As the branched divalent hydrocarbon group, specifically, hydrocarbon groups derived from diamines at both ends of the so-called dimer diamine can be cited. In addition, the so-called dimer diamine is a dimer diamine 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 amino groups as shown in the following formulas (28) to (33) (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.), 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 refers to a carbon-carbon single bond or a carbon-carbon double bond).

[0109] [Chemistry 19]

[0110]

[0111] In addition, 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 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 anhydride, 3,3',4,4'-diphenylsulfonic acid tetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, 3,3',4,4'-biphenyl tetracarboxylic anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro- 2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[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, etc. 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.

[0112] From the viewpoint of solvent solubility of the finally obtained bismaleimide resin, the tetrabasic acid dianhydride (a-3) used for the synthesis of the bismaleimide compound (A) preferably contains a compound selected from the group consisting of the following formulae (11) to (19).

[0113] [Chemistry 20]

[0114]

[0115] In formula (14), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond or a divalent linking group represented by formula (20).

[0116] [Chemistry 21]

[0117]

[0118] 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).

[0119] [Chemistry 22]

[0120]

[0121] 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).

[0122] [Chemistry 23]

[0123]

[0124] 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).

[0125] [Chemistry 24]

[0126]

[0127] 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).

[0128] [Chemistry 25]

[0129]

[0130] 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).

[0131] [Chemistry 26]

[0132]

[0133] 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 crack resistance of the obtained cured product can be further improved, and the required physical properties can be controlled as required.

[0134] The organic diamine (a-2) other than the aromatic diamine (a-1) (hereinafter referred to as the organic diamine (a-2) as appropriate) refers to a diamine other than the diamine contained in the aromatic diamine (a-1) in the present invention. 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'-diaminodiphenyl sulfone; 3,3'-diaminodiphenyl sulfone; 4,4-diaminobenzophenone; 4,4-diaminodiphenyl sulfide; 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 by using these organic diamines (a-2), one of these organic diamines (a-2) may be used alone, or two or more thereof may be used in combination.

[0135] In the resin composition, the content of the bismaleimide 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, relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B), from the viewpoint of achieving better compatibility with the maleimide compound (B) described later, obtaining better heat resistance and thermal stability, and further obtaining a resin composition with good photocurability and crack resistance.

[0136] <Method for producing bismaleimide compound (A)>

[0137] The method for producing the bismaleimide compound (A) is not particularly limited, and the bismaleimide compound (A) can be efficiently produced by, for example, the method shown below.

[0138] As a basic process, a bismaleimide compound can be obtained by synthesizing amic acid from tetrabasic acid dianhydride and diamine and performing ring-closing dehydration through step A, then reacting maleic anhydride to synthesize maleamic acid, and finally performing ring-closing dehydration to cap the molecular chain end with a maleimide group through step B.

[0139] In the production method, each step can be roughly divided into two types: a synthesis reaction of amic acid or maleamic acid and a ring-closing dehydration reaction, which are described in detail below.

[0140] In step A, first, amic acid is synthesized by reacting a specific tetrabasic acid dianhydride with a specific diamine. The reaction is generally carried out in an organic solvent (eg, a nonpolar solvent or a high-boiling-point aprotic polar solvent) at room temperature (25°C) to 100°C.

[0141] Next, the ring-closing dehydration reaction of the amic acid 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.

[0142] Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. These can be used alone or in combination of two or more. In addition, examples of acid catalysts include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. These can be used alone or in combination of two or more.

[0143] The molar ratio of diamine to tetrabasic acid dianhydride is preferably diamine / tetrabasic acid dihydrate = 2.5 to 1.02 / 1.0, more preferably diamine / tetrabasic acid dianhydride = 2.0 to 1.15 / 1.0. By mixing at such a ratio, a copolymer containing amino groups at both ends can be synthesized.

[0144] In step B, maleamic 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, water in the system produced as a by-product is removed under the condition of 95°C to 120°C while performing ring-closing dehydration, thereby capping the molecular chain ends with maleimide groups, and the target bismaleimide compound can be obtained. If the capping reaction of the molecular chain ends with maleimide groups is performed at 120°C or below, side reactions or high molecular weight products are less likely to occur, so it is preferred.

[0145] According to such a production method, the obtained bismaleimide compound has a block copolymer structure, and thus the compatibility with the synthesized resin can be uniformly improved.

[0146] The compound of the present invention may be purified by a conventional method, and reprecipitation or the like may be used.

[0147] 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, it is preferred that (the molar number of the organic diamine (a-2)): (the molar number of the aromatic diamine (a-1)) is greater than 0.1, and more preferably greater than 0.3. In addition, when the organic diamine (a-2) is used, the polymerization form of the amic acid unit containing the aromatic diamine (a-1) and the tetracarboxylic dianhydride (a-3) and the amic acid unit containing the organic diamine (a-2) and the tetracarboxylic dianhydride (a-3) may be random polymerization or block polymerization.

[0148] <Maleimide compound (B)>

[0149] The resin composition contains a maleimide compound (B) (also referred to as component (B)) other than the bismaleimide 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) can be appropriately mixed with one or more of the compounds represented by the following formulas (2) to (8). In addition, in terms of obtaining a resin sheet in which the bismaleimide compound (A) and the maleimide compound (B) have better solubility, better photocurability and suppressed cracking, the following resin composition preferably contains one to two compounds represented by the following formulas (2) to (8) as the maleimide compound (B), and more preferably contains one compound as the maleimide compound (B).

[0150] As described above, generally, the reactivity of the photoradicals of maleimide compounds is very low. However, as described above, the light transmittance of the bismaleimide compound (A) is very excellent. Therefore, by using the maleimide compound (B), the photocuring initiator (C) described later, which is optionally prepared, and the compound (D) containing one or more carboxyl groups described later, together with the bismaleimide compound (A), light fully reaches the photocuring initiator, efficiently causing the photoradical reaction of the maleimide, and various active energy lines can be used for photocuring.

[0151] 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 sufficiently reach the photocuring initiator, and a free radical reaction can be carried out using the free radicals generated by the photocuring initiator, so that photocuring can be carried out in the composition formulated with the maleimide compound (B).

[0152] 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, light curing and thermal stability. Therefore, the resin composition of this embodiment can be used to form a protective film and a rewiring layer.

[0153] Next, the compounds represented by the following formula (2) to (8) contained in the maleimide compound (B) are described.

[0154] (Compound represented by formula (2))

[0155] The compound represented by formula (2) is the following compound.

[0156] [Chemistry 27]

[0157]

[0158] In formula (2), R2, R3, and R4 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.

[0159] The linear or branched alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group, from the viewpoint of exhibiting good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins.

[0160] In addition, among R2, R3, and R4, it is preferred that R2 and R4 are linear or branched alkyl groups having 1 to 6 carbon atoms, and R3 is a hydrogen atom, from the viewpoint of exhibiting better solubility in a solvent.

[0161] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, from the viewpoint of achieving excellent solubility in a solvent, obtaining a more appropriate viscosity, and further suppressing the increase in viscosity of the varnish.

[0162] As the compound represented by formula (2), commercially available products can also be used, for example, BCPH13 (trade name) manufactured by Qunrong Chemical Industry Co., Ltd. represented by formula (39), BCPH01 (trade name) manufactured by Qunrong Chemical Industry Co., Ltd., or BMC X426 (trade name) manufactured by Qunrong Chemical Industry Co., Ltd. represented by formula (40).

[0163] [Chemistry 28]

[0164]

[0165] In formula (39), n is an integer of 1 to 5.

[0166] [Chemistry 29]

[0167]

[0168] In formula (40), n is an integer of 1 to 10.

[0169] (Compound represented by formula (3))

[0170] The compound represented by formula (3) is the following compound.

[0171] [Chemistry 30]

[0172]

[0173] In formula (3), R5 each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 to 10.

[0174] As the maleimide compound represented by the formula (3), a commercially available product may be used, and examples thereof include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by the formula (41).

[0175] [Chemistry 31]

[0176]

[0177] In formula (41), n ​​is an integer of 1 to 10.

[0178] (Compound represented by formula (4))

[0179] The compound represented by formula (4) is the following compound.

[0180] [Chemistry 32]

[0181]

[0182] In formula (4), R6, R7, and R8 each independently represent a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms.

[0183] 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 atoms in these alkyl groups may be substituted by halogen atoms such as fluorine atoms and chlorine atoms, and cyano groups. Among these alkyl groups, methyl, ethyl, isopropyl, and tert-butyl groups are preferred in terms of better photohardening properties, heat resistance, and thermal stability, and better solubility in solvents, methyl, ethyl, isopropyl, and tert-butyl groups are more preferred, methyl, ethyl, and tert-butyl groups are more preferred, and methyl groups are further preferred.

[0184] As the compound represented by formula (4), the compound represented by formula (42) (also referred to as TMDM in this embodiment) is more preferred in terms of better photocurability, heat resistance, and thermal stability, and better solubility in solvents.

[0185] [Chemistry 33]

[0186]

[0187] (Compound represented by formula (5))

[0188] The compound represented by formula (5) is the following compound.

[0189] [Chemistry 34]

[0190]

[0191] In formula (5), R9 each independently represents a hydrogen atom, a methyl group or an ethyl group, and R 10 Each independently represents a hydrogen atom or a methyl group.

[0192] R9 is preferably a methyl group or an ethyl group from the viewpoint of exhibiting good solubility in a solvent, a low boiling point, low water absorption, and good compatibility with other resins.

[0193] As R 10 From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, a hydrogen atom is preferred.

[0194] As the maleimide compound represented by the formula (5), a commercially available product can be used, and an example thereof is BMI-70 (trade name) manufactured by KI Chemical Co., Ltd. represented by the formula (43).

[0195] [Chemistry 35]

[0196]

[0197] (Compound represented by formula (6))

[0198] The compound represented by formula (6) is the following compound.

[0199] [Chemistry 36]

[0200]

[0201] In formula (6), R 11 Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0202] As R 11 From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, a methyl group or an ethyl group is preferred.

[0203] As the maleimide compound represented by the formula (6), a commercially available product may be used, and an example thereof is BMI-80 (trade name) manufactured by KI Chemical Co., Ltd. represented by the formula (44).

[0204] [Chemistry 37]

[0205]

[0206] (Compound represented by formula (7))

[0207] The compound represented by formula (7) is the following compound.

[0208] [Chemistry 38]

[0209]

[0210] In formula (7), R 12 Each independently represents a hydrogen atom or a methyl group. n represents an integer of 1-10.

[0211] As R 12 From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, a hydrogen atom is preferred.

[0212] As n, an integer of 1 to 5 is more preferable from the viewpoint of excellent solubility in a solvent, obtaining a more suitable viscosity, and being able to further suppress the increase in viscosity of the varnish.

[0213] As the maleimide compound represented by the formula (7), a commercially available product may be used, and an example thereof is BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. represented by the formula (45).

[0214] [Chemistry 39]

[0215]

[0216] In formula (45), n is an integer from 1 to 5.

[0217] The compound represented by formula (8) is the following compound.

[0218] [Chemistry 40]

[0219]

[0220] (In formula (8), there are multiple R 13 Each independently represents a hydrogen atom, 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)

[0221] In the formula (8), m is usually 0 to 3, preferably 0 to 2, and more preferably 0. 13 It 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. 13 In the case of an alkyl group having 6 or more carbon atoms, the electrical characteristics may be deteriorated due to molecular vibration when the alkyl group is exposed to high frequencies.

[0222] Compound (8) is more preferably a structure represented by the following formula (46). This is because, in 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 is compared to the para position, resulting in lower crystallinity.

[0223] [Chemistry 41]

[0224]

[0225] (In formula (46), there are multiple R 23 Each independently represents a hydrogen atom, 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)

[0226] R in formula (46) 23 The preferred ranges of m are the same as those in formula (8).

[0227] 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, relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B), from the viewpoint of achieving better compatibility with the bismaleimide compound (A), obtaining better heat resistance and thermal stability, and further obtaining a resin composition with good photocurability and crack resistance.

[0228] The bismaleimide resin (A) and the maleimide resin (B) are characterized by excellent compatibility. In the present application, the term "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) is measured for the curable resin composition. In other words, in the "incompatible" state, the haze is 50 or more when in a liquid state, and in a cured product, multiple Tgs can be measured even if the resins are uniformly mixed.

[0229] The compatibility and haze of the curable resin composition of the present invention were measured in the following manner.

[0230] [Compatibility]

[0231] When the curable resin composition is visually observed, a composition having no precipitates and the like and being able to be applied to a substrate is regarded as having good compatibility, while a composition having precipitates and the like and being difficult to be applied to a substrate is regarded as having poor compatibility.

[0232] [Haze value]

[0233] 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) which is the total amount of light transmitted when the curable resin composition is placed in a corner cell 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. and the diffuse light transmittance (Td) which is diffused and transmitted through the sheet. The total light transmittance (Tt) is the sum of the parallel light transmittance (Tp) which is transmitted in a coaxial state with the incident light and the diffuse light transmittance (Td).

[0234] Haze (H) = Td / Tt×100···(1)

[0235] <Photopolymerization initiator (C)>

[0236] The photopolymerization initiator (C) is not particularly limited, and conventionally used photopolymerization initiators can be appropriately adopted. Examples thereof include acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michelle's ketone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 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-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), 2,4-dimethylthioxanthone and the like photopolymerization initiators. As such a photopolymerization initiator (C), one kind may be used alone, or two or more kinds may be used in combination.

[0237] Among these, as the photopolymerization initiator (C), from the viewpoint that a fine pattern can be formed using a reduced projection exposure machine (stepper; light source wavelength: 365nm, 436nm) which is standardly used in the manufacturing process of a protective film of a semiconductor, etc., it is preferred to use a photopolymerization initiator that efficiently generates free radicals at an exposure wavelength of 310nm to 436nm (more preferably 365nm). In addition, maleimide groups generally do not use free radicals for homopolymerization, and mainly react with free radicals generated by a photopolymerization initiator to form a cross-linked structure by a dimerization reaction of a bismaleimide compound. Therefore, the inventors and others speculate that compared with acrylic compounds and the like generally used as photopolymerizable compounds, bismaleimide compounds are apparently lacking in reactivity. Therefore, from the viewpoint that free radicals can be generated more efficiently and the reactivity at an exposure wavelength of 310nm to 436nm (more preferably 365nm) becomes higher, as the photopolymerization initiator of the present invention, a compound having an oxime structure or a thioxanthone structure is further preferred.

[0238] Examples of such photopolymerization initiators include 1,2-octanedione, 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-dimethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S") having a thioxanthone structure. Such photopolymerization initiators having a high ability to generate free radicals by light tend to have an excessively high reactivity and are difficult to control the reaction when used for photopolymerization of ordinary acrylic compounds, but can be suitably used in the present invention.

[0239] 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 relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving the compatibility with the bismaleimide compound (A) and the maleimide compound (B), allowing the photocuring of these to proceed sufficiently, making the exposed portion sufficiently insolubilized in terms of developability in an organic solvent, and obtaining a resin sheet that can suppress cracking.

[0240] <Compound containing one or more carboxyl groups (D)>

[0241] The resin composition may contain a compound (D) (also referred to as component (D) or compound (D)) containing one or more carboxyl groups. 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 and a potassium salt. When the molecule contains two or more carboxyl groups, it may also be an acid anhydride formed by these mutually linked groups. Compound (D) may also be used alone or in combination of two or more.

[0242] The compound (D) can be photocured together with the bismaleimide compound (A) and the maleimide compound (B) and, if necessary, a photocuring initiator (C) using various active energy rays to obtain a cured product. In addition, a resin composition containing the compound (D) can be obtained in the unexposed portion.

[0243] When preparing a 1% by mass N-methylpyrrolidone solution containing the compound (D), and measuring the transmittance of the 1% by mass N-methylpyrrolidone solution containing the compound (D) using an active energy line containing a wavelength of 365nm (i-ray), the transmittance of the compound (D) is preferably 5% or more. In this way, the compound (D) shows very excellent light transmittance. In addition, when measuring the transmittance of the 1% by mass N-methylpyrrolidone solution containing the compound (D) using an active energy line containing a wavelength of 405nm (h-ray), the transmittance is preferably 5% or more, and the case 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 drawing exposure method, even when an active energy line containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is efficiently caused. For a resin composition having better photocurability, the preferred range of transmittance at a wavelength of 365 nm (i-ray) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more. For a resin composition having 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. In addition, the upper limit of each 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.

[0244] In the present embodiment, it is preferred that the compound (D) contain a carboxyl group at an integer of 2 to 4 in the molecule in order to obtain more excellent alkali developability.

[0245] The molecular weight of the compound (D) is preferably 50 to 1,000, more preferably 100 to 800, from the viewpoint of further improving developability.

[0246] 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) can be used alone or in combination of two or more.

[0247] (Aliphatic compounds containing one or more carboxyl groups)

[0248] As aliphatic compounds containing more than one carboxyl group, for example, chain aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, chain aliphatic polycarboxylic acid, and alicyclic polycarboxylic acid can be listed. These compounds may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl in the molecule. In addition, when these compounds have two or more carboxyl groups in the molecule, they may also be acid anhydrides formed by these mutually linked. When these compounds have carboxylalkyl in the molecule, they may also be acid anhydrides formed by carboxylalkyl and carboxyl groups mutually linked. When these compounds have two or more carboxylalkyl in the molecule, they may also be acid anhydrides formed by these mutually linked.

[0249] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

[0250] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexyloxy group, and a 2-methylpropoxy group.

[0251] Examples of the aryloxy group include a phenoxy group and a p-tolyloxy group.

[0252] Examples of the aryl group include a phenyl group, a toluoyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

[0253] Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, and an aminononyl group.

[0254] Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, and a carboxynonyl group.

[0255] 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.

[0256] 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.

[0257] 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, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

[0258] Examples of the alicyclic polycarboxylic acid include carboxylic acids obtained by further adding one or more carboxyl groups to an alicyclic monocarboxylic acid. For example, monocyclic carboxylic acids such as cyclopropanedicarboxylic acid, cyclopropylenedicarboxylic acid, cyclopropylenetricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutenetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopentenetricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentenetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexanetricarboxylic acid, cyclohexenetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexenetetracarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexenepentacarboxylic acid, cyclohexanehexacarboxylic acid, cyclohexenehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptenedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclooctenedicarboxylic acid; and polycyclic or bridged alicyclic dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid may be mentioned.

[0259] (Aromatic compounds containing one or more carboxyl groups)

[0260] As the parent skeleton of the aromatic compound containing more than one carboxyl group, for example, benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxylbenzene, hexacarboxylbenzene, naphthalenecarboxylic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, and anthracene pentacarboxylic acid, etc. Aromatic compounds may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl on the aromatic rings of these parent skeletons. In addition, these compounds may also be acid anhydrides formed by these mutually linked when they have more than two carboxyl groups in the molecule. These compounds may also be acid anhydrides formed by carboxyl alkyl and carboxyl groups when they have carboxyl alkyl in the molecule. These compounds may also be acid anhydrides formed by these mutually linked when they have more than two carboxyl alkyl in the molecule. Regarding these substituents, reference may be made to the above.

[0261] (Hetero compounds containing more than one carboxyl group)

[0262] As the parent skeleton of the hetero compound containing more than one carboxyl group, for example, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thiophene, phenothiazine, phenoxathiol, xanthene, acridine, phenazine, and carbazole heterocyclic compounds containing more than one carboxyl group. The hetero compound may also have, for example, hydrogen atoms, and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl on these parent skeletons. In addition, these compounds may also be acid anhydrides formed by these mutually linked when they have two or more carboxyl groups in the molecule. These compounds may also be acid anhydrides formed by the mutual linking of carboxyl alkyl and carboxyl groups when they have carboxyl alkyl in the molecule. These compounds may also be acid anhydrides formed by the mutual linking of carboxyl alkyl and carboxyl groups when they have two or more carboxyl alkyl in the molecule. Regarding these substituents, reference can be made to the above description.

[0263] As compound (E), in terms of being able to impart better alkali developability 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). In terms of being able to impart better alkali developability to the resin composition, more preferred is the compound represented by formula (23).

[0264] The compound represented by formula (21) is as follows.

[0265] [Chemistry 42]

[0266]

[0267] 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 can also be an acid anhydride formed by these mutually linked groups. In formula (21), the upper limit of the number of carboxyl groups is 6.

[0268] In terms of alkali developability, R 19 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0269] Furthermore, benzoic acid tends to be inferior in alkali developability compared with other compounds (D) containing one or more carboxyl groups.

[0270] In addition, o each independently represents an integer of 1-5.

[0271] As the compound represented by the formula (21), a compound represented by the formula (47) is preferred in terms of obtaining more excellent alkali developability.

[0272] [Chemistry 43]

[0273]

[0274] In formula (47), R 19 Each independently represents a hydrogen atom, a hydroxyl group, an amino group or an aminomethyl group. 19 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0275] In addition, o each independently represents an integer of 0-4.

[0276] The number of carboxyl groups s represents an integer of 5 to 0. In order to show more excellent alkali developability, the number of carboxyl groups s is preferably an integer of 1 to 3. In this case, R 19 The number o is an integer from 5 to s and is an integer from 2 to 4.

[0277] The compound represented by formula (47) contains two or more carboxyl groups, and these carboxyl groups may be linked to each other to form an acid anhydride.

[0278] 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 these anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. In terms of obtaining better alkali developability, the compound represented by formula (21) is preferably phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof.

[0279] The compound represented by formula (22) is as follows.

[0280] [Chemistry 44]

[0281]

[0282] In formula (22), R 20 Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (22) may be an acid anhydride formed by these mutually linked groups when having two or more carboxyl groups. In formula (22), the upper limit of the number of carboxyl groups is 10. The compound represented by formula (22) may be an acid anhydride formed by carboxymethyl group and carboxyl group when having a carboxymethyl group.

[0283] In terms of alkali developability, R 20 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0284] In addition, p each independently represents an integer of 1-9.

[0285] As R 20 In the case of containing a carboxyl group, the number p of the carboxyl groups is preferably 1 to 3 in terms of alkali developability. 20 , preferably each independently represents 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, R other than the carboxyl group 20 The number is 7 to 9.

[0286] Examples of the compound represented by formula (22) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic anhydride.

[0287] The compound represented by formula (23) is as follows.

[0288] [Chemistry 45]

[0289]

[0290] In formula (23), R21 Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (23) may be an acid anhydride formed by these mutually linked when having two or more carboxyl groups. In formula (23), the upper limit of the number of carboxyl groups is 10. The compound represented by formula (23) may be an acid anhydride formed by carboxymethyl group and carboxyl group mutually linked when having a carboxymethyl group.

[0291] In terms of alkali developability, R 21 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0292] In addition, q each independently represents an integer of 1-9.

[0293] As the compound represented by the formula (23), a compound represented by the formula (48) is preferred in terms of obtaining more excellent alkali developability.

[0294] [Chemistry 46]

[0295]

[0296] In formula (48), R 21 Each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. 21 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0297] In addition, q each independently represents an integer of 0-8.

[0298] The number of carboxyl groups t represents an integer of 9-q. In order to show more excellent alkali developability, the number of carboxyl groups t is preferably an integer of 1 to 3. In this case, R 21 The number q is an integer of 9-t and an integer of 6-8.

[0299] The compound represented by formula (48) contains two or more carboxyl groups, and these groups may be linked to form an acid anhydride. In addition, when the compound represented by formula (48) has a carboxymethyl group, the carboxymethyl group and the carboxyl group may be linked to form an acid anhydride.

[0300] 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 more excellent alkali developability, the compound represented by formula (23) is preferably cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

[0301] The compound represented by formula (24) is as follows.

[0302] [Chemistry 47]

[0303]

[0304] In formula (24), R 22 Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (24) may be an acid anhydride formed by the mutual connection of a carboxyl group and a carboxyl group when having more than one carboxyl group. In addition, in formula (24), when having more than two carboxyl groups, it may be an acid anhydride formed by these mutual connection. In formula (24), the upper limit of the number of carboxyl groups is 5. In formula (24), when having more than two carboxylmethyl groups, it may be an acid anhydride formed by these mutual connection. In formula (24), the upper limit of the number of carboxyl groups is 6.

[0305] In terms of alkali developability, R 22 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0306] In addition, r each independently represents an integer of 1-5.

[0307] As the compound represented by the formula (24), a compound represented by the formula (49) is preferred in terms of obtaining more excellent alkali developability.

[0308] [Chemistry 48]

[0309]

[0310] In formula (49), R 22 Each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. 22 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0311] In addition, r each independently represents an integer of 0-4.

[0312] The number u of carboxyl groups represents an integer of 5-r. In terms of showing more excellent alkali developability, the number u of carboxyl groups is preferably an integer of 1 to 3. In this case, the number r of R7 is an integer of 5-u and an integer of 2 to 4.

[0313] In formula (49), it can also be an acid anhydride formed by the mutual connection of a carboxymethyl group and a carboxyl group. When the compound represented by formula (49) has two or more carboxyl groups, it can also be an acid anhydride formed by these mutual connection. 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, it can also be an acid anhydride formed by these mutual connection. In formula (49), the upper limit of the number of carboxymethyl groups is 6.

[0314] Examples of the compound represented by formula (24) include phenyleneacetic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, and anhydrides thereof. Examples of the anhydrides thereof include 1,2-phenylenediacetic acid anhydride. As the compound represented by formula (24), 1,2-phenylenediacetic acid is preferred in terms of obtaining better alkali developability.

[0315] These compounds (D) containing one or more carboxyl groups can also be used alone or in combination of two or more.

[0316] In the resin composition, the content of the compound (D) containing 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 relative to 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B), from the viewpoint of improving the compatibility with the bismaleimide compound (A) and the maleimide compound (B), further reducing the liquid component in the varnish, and providing better alkali developability.

[0317] <Compound (E) reactive with maleimide group other than bismaleimide compound (A) and maleimide compound (B)>

[0318] The resin composition may contain a maleimide compound other than the bismaleimide compound (A) and the maleimide compound (B), a cyanate compound, a phenol resin, an epoxy resin, an oxetane resin, a benzoxazine compound, a carbodiimide compound, and a compound having an ethylenically unsaturated group as a compound (E) that can react with a maleimide group other than the bismaleimide compound (A) and the maleimide compound (B).

[0319] (Maleimide compounds other than the bismaleimide compound (A) and the maleimide compound (B))

[0320] As other maleimide compounds, as long as they are compounds other than the bismaleimide compound (A) and the maleimide compound (B) and having one or more maleimide groups in the molecule, there is no particular limitation. As specific examples thereof, 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 biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimidoethane , 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl) hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis(3 -maleimide phenoxy) benzene, 1,3-bis(4-maleimide phenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimide phenoxy) phenyl] propane, bis(3,5-dimethyl-4-citraconimide phenyl) methane, bis(3-ethyl-5-methyl-4-citraconimide phenyl) methane, bis(3,5-diethyl-4-citraconimide phenyl) methane, polyphenylmethane maleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds can also be used alone or in combination of two or more.

[0321] In the resin composition, the total content of other maleimide compounds 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.

[0322] (Cyanate ester compound)

[0323] The cyanate compound is a cyanate compound obtained by reacting a phenol resin with a cyanogen halide, and specific examples thereof 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)sulfone, bis(4-cyanate phenyl)sulfide, phenol novolac cyanate, and a cyanate compound obtained by converting a hydroxyl group of a phenol-dicyclopentadiene co-condensate into a cyanate group, but the present invention is not limited thereto.

[0324] In addition, the cyanate compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferred because of its low hygroscopicity, flame retardancy, and excellent dielectric properties.

[0325] In order to trimerize the cyanate group to form a s-triazine ring as needed, the cyanate compound may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, etc. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, relative to 100 parts by mass of the total mass of the composition.

[0326] In the composition, the total content of the cyanate ester compounds 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.

[0327] (Phenolic resin)

[0328] As the phenol resin, any generally known phenol resin can be used as long as it is a phenol resin having 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, multifunctional phenol resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, and hydroxyl-containing silicone resins, etc. can be listed, but there is no particular limitation. These phenol resins can be used alone or in combination of two or more.

[0329] In the composition, the total content of the phenol resin 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.

[0330] (Epoxy resin)

[0331] The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylene novolac epoxy resin, multifunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolac epoxy resin, naphthalene ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, tetrafunctional phenol epoxy resin, triglycidyl isocyanurate epoxy resin, Ester, glycidyl ester epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, phenol aralkyl novolac epoxy resin, naphthol aralkyl novolac epoxy resin, aralkyl novolac epoxy resin, naphthol aralkyl novolac epoxy resin, dicyclopentadiene epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, compounds obtained by epoxidizing double bonds of butadiene, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can also be used alone or in combination of two or more.

[0332] In the composition, the total content of the epoxy resin 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.

[0333] (Oxetane resin)

[0334] As the oxetane resin, generally known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), and OXT-121 (manufactured by Toagosei Co., Ltd., trade name), etc., can be listed, but there is no particular limitation. These oxetane resins can also be used alone or in combination of two or more.

[0335] In the composition, the total content of the oxetane resin is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the composition of the present embodiment.

[0336] (Benzoxazine compounds)

[0337] As the benzoxazine compound, any generally known benzoxazine compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein benzoxazine, etc. can be cited, but there is no particular limitation. These benzoxazine compounds can also be used alone or in combination of two or more.

[0338] In the composition, the total content of the benzoxazine compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the composition of the present embodiment.

[0339] (Carbodiimide compound)

[0340] The carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group in the molecule, and generally known carbodiimide compounds 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 mentioned. These carbodiimide compounds can be used alone or in combination of two or more.

[0341] In the composition, the total content of the carbodiimide compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the composition of the present embodiment.

[0342] (Compound having ethylenically unsaturated group)

[0343] The compound having an ethylenically unsaturated group is not particularly limited as long as it has an ethylenically unsaturated group in one molecule.

[0344] 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, butanediol 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, and the like. alcohol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalate neopentyl glycol di(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane 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.

[0345] In addition, as specific examples of compounds having ethylenically unsaturated groups, urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy (meth)acrylates derived from epoxy resins and having both a (meth)acryloyl group; reactive oligomers using these bonds in combination, etc. can also be listed.

[0346] Examples of the urethane (meth)acrylates include reaction products of a hydroxyl group-containing (meth)acrylate, a polyisocyanate, and other alcohols used as necessary. 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; and urethane (meth)acrylates obtained by reacting sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate with toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane hexamethylene diisocyanate, and polyisocyanates such as isocyanurates and biuret reaction products thereof.

[0347] The 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, and caprolactone-modified (meth)acrylate tetrahydrofurfuryl; di(poly)ester (meth)acrylates such as hydroxypivalate neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalate neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono-, di-, or tri(meth)acrylates of triols obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of trimethylolpropane or glycerol.

[0348] In addition, examples include: 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 and δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane or tetramethylolpropane; mono-(meth)acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone and δ-valerolactone to 1 mol of dipentaerythritol; or mono- or poly-(meth)acrylates of triols, tetraols, pentaols or hexaols of polyols such as poly(meth)acrylates.

[0349] Furthermore, examples include: (meth)acrylates of polyester polyols which are 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 polybasic acids 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 sulfoisophthalic acid, and acid anhydrides thereof; and polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of polyester diols modified with diol components, polybasic acids, and acid anhydrides thereof, and cyclic lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone.

[0350] The epoxy (meth) acrylates refer to carboxylic acid ester compounds of compounds having an epoxy group and (meth) acrylic acid. Examples thereof include phenol novolac epoxy (meth) acrylates, cresol novolac epoxy (meth) acrylates, trihydroxyphenylmethane epoxy (meth) acrylates, dicyclopentadienephenol epoxy (meth) acrylates, bisphenol F epoxy (meth) acrylates, bisphenol A novolac epoxy (meth) acrylates, naphthalene skeleton-containing epoxy (meth) acrylates, glyoxal epoxy (meth) acrylates, heterocyclic epoxy (meth) acrylates, and anhydride-modified epoxy acrylates thereof.

[0351] 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 bisallyl nadic imide are also listed as specific examples of compounds having an ethylenically unsaturated group.

[0352] 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) 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-8002H, 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 an ethylenically unsaturated group may be used alone or in combination of two or more.

[0353] 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.

[0354] <Hardening accelerator (F)>

[0355] The resin composition may further contain a hardening accelerator (F). For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine; organic metal salts such as tin octanoate, zinc octanoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Lewis acids such as boron trifluoride. acid); salts such as sodium carbonate or lithium chloride, etc.

[0356] Specific examples of the hardening accelerator (F) are shown below.

[0357] Examples of the organic peroxide polymerization initiator include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)cyclohexane, 1,1-bis(tert-hexylperoxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxide)cyclohexane, 2,2-bis(4,4-di-tert-butylperoxide)cyclohexyl)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-butyl 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)hexyne-3, isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxide Peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, α,α'-bis(peroxyneodecanoyl) 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 peroxyneodecanoate 、1-cyclohexyl-1-peroxymethylethyl-2-ethylhexanoate, tert-hexyl peroxide-2-ethylhexanoate, tert-butyl 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(peroxy-butyl)isophthalate, tert-butyl peroxide-allyl monocarbonate, 3,3',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, etc.

[0358] Examples of azo 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[N-(4-hydroxyphenyl)-2-methylpropanamide] dihydrochloride, 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-( ... Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazolin-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.

[0359] Furthermore, as a hardening accelerator (F), for example, a phosphine compound, a compound having a phosphonium salt, an imidazole compound, etc. can be listed, and one of these can be used or two or more can be used in combination. Among them, an imidazole compound is preferred. Imidazole compounds have particularly excellent functions as catalysts, and therefore can more effectively promote the polymerization reaction of bismaleimide resin (A) and maleimide resin (B).

[0360] 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-methyl-imidazole, 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 between 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 can be used alone or in combination of two or more.

[0361] 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; and tertiary phosphines 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-phenylphenyl phosphine, tri(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenyl phosphine, tri-4-methoxyphenyl phosphine, and tri-2-cyanoethyl phosphine. Among them, tertiary phosphines can be preferably used. These can be used alone or in combination of two or more.

[0362] 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.

[0363] 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, relative to 100 parts by mass of the total amount of the reactive resin component.

[0364] The resin composition may contain, as components (F) other than essential components, for example, inorganic fillers, release agents, flame retardants, ion scavengers, antioxidants, adhesives, stress reducing agents, colorants, and coupling agents within a range that does not impair the effects of the present invention.

[0365] (Filling material)

[0366] The curable resin composition of the present invention may further contain a filler in order to improve coating properties, heat resistance, etc. The filler preferably has insulating properties and does not inhibit the transmittance of the wavelength 405 nm (h-ray). As fillers, there is no particular limitation, and examples thereof include: silica (e.g., natural silica, fused silica, synthetic silica, hollow silica, etc.), aluminum compounds (e.g., diaspore, 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., short glass fibers, spherical glass, glass fine powder (e.g., E glass, T glass, D glass, etc.), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth) acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers can also be used alone or in combination of two or more.

[0367] Among these, preferably, one or more selected from the group consisting of silica, diaspore, barium sulfate, silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber.

[0368] These fillers may be surface-treated with a silane coupling agent or the like described below.

[0369] In terms 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 silica is more preferred. As specific examples of silicon dioxide, SFP-130MC manufactured by Denka (stock), SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatechs (stock) can be cited.

[0370] The particle size of the filler is not particularly limited, but is usually 0.005 μm to 100 μm, preferably 0.01 μm to 50 μm.

[0371] In the resin composition, the content of the filler is not particularly limited. From the viewpoint of making the heat resistance of the cured product good, it is preferably set to 1000 parts by mass or less, more preferably to 500 parts by mass or less, and most preferably to 300 parts by mass or less, relative to 100 parts by mass of the resin solid component in the resin composition. In addition, when the filler is contained, the lower limit is not particularly limited. From the viewpoint of obtaining the effect of improving the coating properties, heat resistance and other properties, it is usually 1 part by mass relative to 100 parts by mass of the resin solid component in the resin composition.

[0372] (Silane coupling agent and wetting and dispersing agent)

[0373] In the resin composition, a silane coupling agent and / or a wetting dispersant may be used in combination in order to improve the dispersibility of the filler and the bonding strength between the polymer and / or resin and the filler.

[0374] There are no particular limitations on these silane coupling agents as long as they are generally used for surface treatment of inorganic substances. 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, [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; vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxysilane 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; mercaptosilane series such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilane series such as 3-ureidopropyltriethoxysilane; styrylsilane series such as p-styryltrimethoxysilane; cationic silane series such as N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride; acid anhydride series such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilane series such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; arylsilane series such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in combination of two or more.

[0375] 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 content in the resin composition. As a wetting dispersant, as long as it is a dispersion stabilizer used in coating applications, it is not particularly limited. As a specific example, for example, wetting dispersants such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, W903 manufactured by BYK Chemie Japan Co., Ltd. can be cited. These wetting dispersants can also be used alone or in a suitable mixture of two or more.

[0376] In the resin composition, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0377] <Organic solvent (G)>

[0378] 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. The type of organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition.

[0379] Examples of such organic solvents include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isopentyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene, etc.

[0380] Among these, cyclopentanone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred in terms of excellent solubility in other resins and compounds such as bismaleimide compound (A) and maleimide compound (B), and further photopolymerization initiator (C) and compound (D) containing one or more carboxyl groups, and easy preparation of varnish with good solubility. These organic solvents can also be used alone or in combination of two or more.

[0381] [Method for producing resin composition]

[0382] The resin composition is prepared by appropriately mixing a bismaleimide compound (A), a maleimide compound (B), a photocuring initiator (C), and a compound (D) containing one or more carboxyl groups 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.

[0383] The resin composition can be prepared by, for example, sequentially mixing the above components in a solvent and stirring the mixture sufficiently. The resin composition has excellent photocurability, and a cured product obtained from the resin composition has excellent heat resistance, thermal stability, and insulation reliability.

[0384] When manufacturing resin composition, known treatment (stirring, mixing, kneading treatment, etc.) for making each component uniformly dissolve or disperse can be carried out as needed. Specifically, by using a stirring tank equipped with a stirrer with appropriate stirring ability to carry out stirring and dispersing treatment, the dispersibility of each component in the resin composition can be improved. Stirring, mixing, and kneading treatment can be appropriately carried out 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 revolution or autogenous type. In addition, when preparing resin composition, organic solvents can be used as needed. About the type of organic solvent, as long as it can dissolve the resin in the resin composition, it is not particularly limited, and its specific example is as described above.

[0385] The resin composition can be suitably used as a varnish when making the resin sheet of the present embodiment described later. The varnish can be obtained by a known method. For example, the varnish can be obtained by the following method: relative to 100 parts by mass of the components other than the organic solvent in the resin composition of the present embodiment, 10 parts by mass to 900 parts by mass of an organic solvent are added, and the known mixing treatment (stirring, kneading treatment, etc.) is performed.

[0386] [use]

[0387] The resin composition can be preferably used for the purpose of the resin composition requiring insulation reliability. As a purpose, for example, it can be used for a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, a circuit substrate (laminated board purposes, multilayer printed wiring board purposes, etc.), a solder resist, a bottom filling (underfill) material, a crystal bonding material, a semiconductor sealing material, a hole-filling resin, and a component embedding resin, etc. Among these, the resin composition can be suitably used as an insulating layer purpose or a solder resist purpose of a multilayer printed wiring board due to its excellent light curing, heat resistance and thermal stability.

[0388] [Hardened material]

[0389] 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 region of the light, it is preferred to cure within a range of 100 nm to 500 nm, which is a region where curing is efficiently performed by a photopolymerization initiator or the like.

[0390] [Resin sheet]

[0391] The resin sheet of this embodiment is a resin sheet with a support, which has a support and a resin layer disposed on one or both sides of the support, and the resin layer contains a resin composition. The resin sheet can be manufactured by coating the resin composition on the support and drying it. The resin layer in the resin sheet has excellent heat resistance, thermal stability and insulation reliability.

[0392] The support may be a known support, 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 triacetyl acetate film. Among these, a PET film is preferred.

[0393] 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, there is a tendency that the support is easily broken when the support is peeled off before development, and if the thickness exceeds 100 μm, there is a tendency that the resolution when the support is exposed is reduced.

[0394] Furthermore, in order to reduce light scattering during exposure, the resin film is preferably a film having excellent transparency.

[0395] Furthermore, in the resin sheet, the resin layer may be protected by a protective film.

[0396] By protecting the resin layer side with a protective film, dust or the like can be prevented from adhering 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, 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 cheapness tends to be deteriorated. In addition, the protective film is preferably relatively small in adhesion between the resin layer and the support, and the adhesion between the resin layer and the protective film is small.

[0397] Examples of the method for producing the resin sheet include a method in which the resin composition of the present embodiment is applied to a support such as a PET film and then dried to remove the organic solvent, thereby producing the resin sheet.

[0398] The coating method may be, for example, a known method using a roll coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a knife coater, an extrusion coater, etc. Drying may be performed, for example, by heating in a dryer at 60° C. to 200° C. for 1 minute to 60 minutes.

[0399] The amount of organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer from the viewpoint of preventing diffusion of the organic solvent in subsequent steps. The thickness of the resin layer is preferably 1 μm to 50 μm from the viewpoint of improving workability.

[0400] The resin sheet can be preferably used for producing an insulating layer of a multilayer printed wiring board.

[0401] [Multilayer printed wiring board]

[0402] The multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition. For example, one or more resin sheets can be overlapped and hardened to obtain an insulating layer. The number of layers of the insulating layer and the conductor layer is not particularly limited, and the number of layers can be appropriately set according to the target use. In addition, the order of the insulating layer and the conductor layer is not particularly limited. As a conductor 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. As a copper metal foil, copper foils such as rolled copper foil and electrolytic copper foil can be listed. The thickness of the conductor layer is generally 1μm to 100μm. Specifically, it can be manufactured by the following method.

[0403] (Lamination process)

[0404] In the lamination process, a vacuum laminator is used to laminate the resin layer side of the resin sheet on one or both sides of the circuit substrate. As the circuit substrate, for example, glass epoxy substrate, metal substrate, ceramic substrate, silicon substrate, semiconductor sealing resin substrate, polyester substrate, polyimide substrate, bismaleimide triazine (BT) resin substrate, and thermosetting polyphenylene ether substrate can be cited. In addition, the so-called circuit substrate refers to a substrate having a conductor layer (circuit) processed with patterns formed on one or both sides of the substrate. In addition, in a multilayer printed wiring board formed by alternately stacking a conductor layer and an insulating layer, a substrate in which a single side or both sides of the outermost layer of the multilayer printed wiring board become a conductor layer (circuit) processed with patterns is also included in the circuit substrate. In addition, the insulating layer stacked on the multilayer printed wiring board can be an insulating layer obtained by overlapping one or more of the resin sheets of the present embodiment and hardening, or it can be an insulating layer obtained by overlapping one or more of the resin sheets of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. In addition, the overlapping method of the resin sheet of the present embodiment and the known resin sheet that is different from the resin sheet of the present embodiment is not particularly limited. On the conductor layer surface, roughening treatment can also be implemented in advance by blackening treatment and / or copper etching. In the lamination process, when the resin sheet has a protective film, the protective film is peeled off and removed, and the resin sheet and the circuit substrate are preheated as needed, and the resin layer of the resin sheet is pressurized and heated while being crimped to the circuit substrate. In the present embodiment, the method that the resin layer of the resin sheet is laminated to the circuit substrate under reduced pressure by vacuum lamination can be suitably used.

[0405] The conditions of the lamination process are preferably, for example, a pressure bonding temperature (lamination temperature) of 50° C. to 140° C. and a pressure bonding pressure of 1 kgf / cm 2 ~15kgf / cm 2 , the pressing time is set to 5 seconds to 300 seconds, and the air pressure is set to 20 mmHg or less under reduced pressure for lamination. In addition, the lamination process can be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a two-stage build-up laminator (2stage build-up laminator) (trade name) manufactured by Nikko Materials (stock) can be cited.

[0406] (Exposure process)

[0407] In the exposure step, after the resin layer is provided on the circuit board in the lamination step, an active energy line as a light source is irradiated to a predetermined portion of the resin layer to cure the resin layer in the irradiated portion.

[0408] Irradiation can be performed through a mask pattern or by direct irradiation. Examples of active energy rays include ultraviolet rays, visible light rays, electron beams, and X-rays. The wavelength of the active energy rays is, for example, in the range of 200 nm to 600 nm. When ultraviolet rays are used, the irradiation amount is approximately 10 mJ / cm 2 ~1000mJ / 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 line having a wavelength of 365 nm (i-ray), for example. When using an active energy line having a wavelength of 365 nm (i-ray), the irradiation amount is approximately 10 mJ / cm 2 ~10,000mJ / cm 2 When a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured by direct drawing exposure method, it is preferable to use an active energy line having a wavelength of 405nm (h-ray), for example. When using an active energy line having a wavelength of 405nm (h-ray), the irradiation amount is approximately 10mJ / cm 2 ~10,000mJ / cm 2 .

[0409] The exposure method via the mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which parallel light is used for exposure without close contact. Either method can be used. In addition, when a support is present on the resin layer, exposure can be performed from the support, or exposure can be performed after the support is peeled off.

[0410] (Development Process)

[0411] In this embodiment, a developing step may be included as necessary.

[0412] That is, when there is no support on the resin layer, after the exposure step, the un-photocured 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 un-photocured portion (unexposed portion) is removed by wet development and developed, thereby forming a pattern of the insulating layer.

[0413] 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.

[0414] In addition, as a developing method, for example, it can be carried out by known methods such as dipping, coating, spraying, shaking dipping, brushing, scraping, etc. In pattern formation, these developing methods can also be used together as needed. In addition, as a developing method, it is suitable to use high-pressure spray because it will further improve the resolution. As the spray pressure when using the spray method, it is preferably 0.02MPa to 0.5MPa.

[0415] (Post-baking process)

[0416] After the exposure process or the development process, a post-baking process is performed to form an insulating layer (hardened material). As the post-baking process, there are ultraviolet irradiation processes using high-pressure mercury lamps, heating processes using clean ovens, etc., and these processes can also be used in combination. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, 50mJ / cm 2 ~10,000mJ / cm 2 The heating conditions can be appropriately selected as needed, but are preferably in the range of 150°C to 300°C for 20 minutes to 180 minutes, and more preferably in the range of 200°C to 300°C for 30 minutes to 60 minutes.

[0417] (Conductor layer forming step)

[0418] 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. The evaporation method (vacuum evaporation method) is, for example, to place a multilayer printed wiring board in a vacuum container and heat and evaporate the metal, thereby forming a metal film on the insulating layer. The sputtering method is, for example, to place a multilayer printed wiring board in a vacuum container, introduce an inert gas such as argon and apply a DC voltage, so that the ionized inert gas collides with the target metal, and a metal film can be formed on the insulating layer by using the knocked-out metal.

[0419] Then, a conductor layer is formed by electroless plating or electrolytic plating, etc. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. can be used.

[0420] [Sealing materials]

[0421] The sealing material of the present embodiment includes the resin composition of the present embodiment. As the manufacturing method of the sealing material, generally known methods can be appropriately applied, and there is no particular limitation. For example, the sealing material can be manufactured by mixing the resin composition of the present embodiment with various known additives or solvents generally used in the sealing material use using a known mixer. In addition, during mixing, the maleimide compound of the present embodiment, various additives, and the method for adding the solvent can appropriately apply generally known methods, and there is no particular limitation.

[0422] [Fiber-reinforced composite materials]

[0423] The fiber-reinforced composite material of the present embodiment comprises the resin composition of the present embodiment and reinforcing fibers. As reinforcing fibers, generally known reinforcing fibers 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; polyaramid fibers; boron fibers; poly-p-phenylene benzobisoxazole (PBO) fibers; high-strength polyethylene fibers; alumina fibers; silicon carbide fibers. There are no particular limitations on the form and arrangement of the reinforcing fibers, and they can be appropriately selected from fabrics, non-woven fabrics, felts, knitted fabrics, ribbons, unidirectional strands, rovings, and chopped materials. In addition, as the form of reinforcing fibers, preforms (reinforcing fibers formed by laminating fabric base fabrics containing reinforcing fibers or reinforcing fibers formed by sewing them together using sutures, or fiber structures such as three-dimensional fabrics or woven fabrics) can also be used.

[0424] As a method for manufacturing 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 can be cited. Among these, the resin transfer molding method, which is one of the liquid composite molding methods, can pre-set raw materials other than preforms such as metal plates, foam cores, and honeycomb cores in the forming mold, so it can cope with various uses, so it can be preferably used in the case of mass production of composite materials with relatively complex shapes in a short time.

[0425] [Adhesive]

[0426] The adhesive of the present embodiment includes the resin combination of the present embodiment. As the manufacturing method of the adhesive, generally known methods can be appropriately applied, and are not particularly limited. For example, the adhesive can be manufactured by mixing the resin combination of the present embodiment with various known additives or solvents generally used in the adhesive purposes using a known mixer. In addition, during mixing, the maleimide compound of the present embodiment, various additives, and the method for adding the solvent can appropriately apply generally known methods, and are not particularly limited.

[0427] [Semiconductor devices]

[0428] The heat-resistant resin film formed by the resin composition of the present invention can be used for 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 insulating films, insulating films of redistribution layers, interlayer insulating films of multilayer wiring for high-density mounting, interlayer insulating films of electronic parts such as inductors or surface acoustic wave (SAW) filters, and insulating films or planar layers of organic electric field light-emitting elements, but it is not limited thereto, and various structures can be adopted.

[0429] The compounds and compositions of the present invention can also be used in the form of dry film resists. That is, for the compounds and compositions of the present invention, after the compounds and compositions are applied to the base film using a roll coater, a die coater, a blade coater, a rod coater, a gravure coater, etc., they are dried in a drying oven set at 45°C to 140°C, and a prescribed amount of solvent is removed, or a cover film is stacked as needed, thereby making a dry film resist. At this time, the thickness of the resist on the base film is adjusted to 2μm to 200μm. As a base film and a cover film, for example, films of polyester, polypropylene, polyethylene, triacetylcellulose (TAC), polyimide, etc. are used. Among these films, films treated with a silicone release agent or a non-silicone release agent can also be used as needed. If supplied as a dry film resist, the coating and drying steps on the support can be omitted, and the photosensitive resin composition of the present invention can be used more simply.

[0430] Example

[0431] 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 loss temperature (Td5)), and crack resistance after photopatterning in each example and comparative example were evaluated in the following manner.

[0432] The conditions for measuring the molecular weight are as follows.

[0433] Model: GPC TOSOH HLC-8220GPC

[0434] Column: Super HZM-N

[0435] Eluent: tetrahydrofuran (THF); 0.35 ml / min, 40 °C

[0436] Detector: Differential refractometer (refractive index, RI)

[0437] Molecular weight standard: polystyrene

[0438] <Bismaleimide compound (A)>

[0439] Synthesis Example 1 (A-1)

[0440] In a 1L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark device, powder inlet, nitrogen inlet device and stirring device, 165g of toluene and 165g of N-methylpyrrolidone were added. Next, 26.6g (0.20mol) of m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 11.7 (0.02mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9g (0.22mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (48.2g, 0.11mol) was slowly added to the stirred mixture. The mixture was heated to reflux 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 generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of the bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby implementing a reprecipitation process, removing the solvent and drying it, thereby obtaining the target light brown solid bismaleimide compound 72 g (yield 72%, Mw = 4,000) (A-1).

[0441] Synthesis Example 2 (A-2)

[0442] In a 1L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark device, powder inlet, nitrogen inlet device and stirring device, 165g of toluene and 165g of N-methylpyrrolidone were added. Next, 26.6g (0.20mol) of m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 23.4 (0.04mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9g (0.22mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (48.2g, 0.11mol) was slowly added to the stirred mixture. The mixture was heated to reflux 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 generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of a bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby implementing a reprecipitation process, removing the solvent and drying it, thereby obtaining 72 g (yield 72%, Mw = 4,000) of the target light brown solid bismaleimide compound (A-2).

[0443] Synthesis Example 3 (A-3)

[0444] In a 1L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark device, powder inlet, nitrogen inlet device and stirring device, 165g of toluene and 165g of N-methylpyrrolidone were added. Next, 26.6g (0.20mol) of m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 35.1 (0.06mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9g (0.22mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (48.2g, 0.11mol) was slowly added to the stirred mixture. The mixture was heated to reflux 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 generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of the bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby implementing a reprecipitation process, removing the solvent and drying it, thereby obtaining the target light brown solid bismaleimide compound 72 g (yield 72%, Mw = 4,000) (A-3).

[0445] <Maleimide compound (B)>

[0446] As the maleimide compound (B), the following four compounds were prepared.

[0447] (B-1) Maleimide compound

[0448] Manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000"

[0449] (B-2) Maleimide compound

[0450] Manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-5000"

[0451] (B-3) Maleimide compound

[0452] Manufactured by KI Chemical, trade name "BMI-70"

[0453] (B-4) Maleimide compound

[0454] Made by Yamato Kasei Kogyo Co., Ltd., trade name "BMI-2300"

[0455] <Photopolymerization initiator (C)>

[0456] Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE-02")

[0457] (Examples 1 to 10 and Comparative Examples 1 to 6)

[0458] The components (A) to (C) in the amounts (parts by mass) shown in Tables 1 and 2 and 103 parts by mass of cyclopentanone as an organic solvent (G) were mixed to prepare photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6.

[0459] <Characteristics Evaluation>

[0460] The following properties were measured for the produced curable resin composition and cured film.

[0461] [Compatibility]

[0462] The visual compatibility refers to the state of the curable resin composition after mixing components (A) to (G) and stirring. Good compatibility means that there is no precipitate and it can be coated on the substrate, while poor compatibility means that there is precipitate and it is difficult to coat on the substrate.

[0463] (Evaluation Criteria)

[0464] ○: No precipitates

[0465] ×: There is precipitate

[0466] [Photopatterning evaluation]

[0467] 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 film with a thickness of 10 μm to 15 μm. Subsequently, a "Ultra-High Pressure Mercury Lamp 500W 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.

[0468] The crack resistance was determined by observing the pattern after development under a microscope to determine whether cracks were generated on the pattern.

[0469] (Crack resistance evaluation criteria)

[0470] ○: No cracks

[0471] ×: There are cracks

[0472] In addition, the curability is also determined by whether or not a pattern remains after development.

[0473] (Light-hardening criteria)

[0474] ○: After development, the pattern remains

[0475] ×: No residue left after development

[0476] Table 1 shows the results of crack resistance and light curing properties.

[0477] [Dielectric properties]

[0478] First, the photosensitive resin composition obtained in each embodiment and comparative example is applied to 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 is adjusted so that the film thickness of the dried film-like photosensitive resin composition becomes 20 μm. A light source capable of irradiating active energy rays having a wavelength of 405 nm (h-rays) (Ultra-high pressure mercury lamp 500W MultiLight (MultiLight) (trade name) manufactured by USHIO (stock)) is used, with an exposure amount of 3000 mJ / cm 2 The film-like photosensitive resin composition is exposed, and then, after being hardened by heating at a temperature of 250°C for 60 minutes under a nitrogen environment, the copper foil is removed by etching to obtain a cured film. The cured product of the resin film is cut to make a test piece of 80mm×3mm. For the obtained test piece, after being placed in an environment of 25°C 20% for one day, the relative dielectric constant and dielectric loss tangent at 10GHz are measured by a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.). For the measuring instrument, a vector network analyzer ADMSO10c1 manufactured by AET was used, and for the cavity resonator, a CP531 (10GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd. was used. The results are shown in Table 1.

[0479] [Glass transition temperature (Tg) evaluation]

[0480] The photosensitive resin composition obtained in each embodiment and comparative example was applied to 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 dried film-like photosensitive resin composition was 20 μm. A light source capable of irradiating active energy rays having a wavelength of 405 nm (h-rays) (Ultra-high pressure mercury lamp 500W MultiLight (MultiLight) (trade name) manufactured by USHIO (stock)) was used, with an exposure amount of 3000 mJ / cm 2 The film-like photosensitive resin composition was exposed to light, and then heated and cured at a temperature of 250° C. for 60 minutes in a nitrogen atmosphere, and then the copper foil was removed by etching to obtain a cured film.

[0481] The dynamic viscoelasticity of the cured product of the bismaleimide 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 by 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.

[0482] [Resistance to thermal decomposition]

[0483] The photosensitive resin composition obtained in each embodiment and comparative example was applied to 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 dried film-like photosensitive resin composition was 20 μm. A light source capable of irradiating active energy rays having a wavelength of 405 nm (h-rays) (Ultra-high pressure mercury lamp 500W MultiLight (MultiLight) (trade name) manufactured by USHIO (stock)) was used, with an exposure amount of 3000 mJ / cm 2The film-like photosensitive resin composition was exposed, and then heated at 250°C for 60 minutes in a nitrogen environment to cure, and then the copper foil was 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 in a measuring pan, and the 5% weight reduction rate (Td5) was measured under the conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. The measuring device used was a thermogravimetric analysis / differential scanning calorimeter (TGA / DSC) 1 (manufactured by METTLER TOLEDO).

[0484] [Table 1]

[0485]

[0486] [Table 2]

[0487] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative 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 〇 〇 〇 〇 Light curing × × × × Cracking resistance -* -* -* -* Heat resistance(℃) -* -* -* -* Dielectric constant (Dk) -* -* -* -* Dielectric loss tangent (Df) -* -* -* -* Td5(℃) -* -* -* -*

[0488] *: The light curing property is low and a cured film cannot be produced, so it cannot be evaluated.

[0489] As is clear from the results shown in Table 1, by using the photosensitive resin composition of the present invention, an excellent cured product having good compatibility, light curing properties, and crack resistance, low dielectric properties, a high glass transition temperature of 200° C. or higher, and high thermal decomposition resistance of 380° C. or higher can be obtained.

[0490] Industrial Applicability

[0491] As described above, the present invention can form fine patterns with relatively low exposure (below 2000mJ / cm2), and can obtain a resin sheet having a high glass transition temperature (Tg) of above 200°C, high thermal decomposition resistance of above 380°C, a good dielectric loss tangent of below 0.006, and good crack resistance.

[0492] Therefore, the bismaleimide compound and the photosensitive resin composition of the present invention are very useful as a surface protective film of a semiconductor element, an interlayer insulating film, an insulating film of a redistribution layer, and the like.

Claims

1. A resin composition comprising: 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); [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), R2, R3, and R4 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), R5 each independently represents a hydrogen atom or a methyl group; n represents an integer of 1 to 10); [Chemistry 4] (In formula (4), R6, R7, and R8 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, R 10 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; n4 represents an integer from 1 to 10); [Chemistry 8] (In formula (8), there are multiple R 13 (a) each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; m represents an integer of 0 to 3; and n is a repeating number, the average value of which is 1<n<5).

2. A resin composition comprising: a bismaleimide compound (A) represented by the following formula (9); and a maleimide compound (B) selected from at least one of 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); [Chemistry 9] (In formula (9), R 16 independently represent a tetravalent organic group containing a cyclic structure; R 15 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 14 are independently represented by the following formula (10); R 17 For R 14 or R 16 ; m is 1 to 100, n is 0 to 100; in addition, the order of the repeating units enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random; [Chemistry 10] (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).

3. The resin composition according to claim 1, comprising the bismaleimide compound (A) wherein the tetrabasic acid dianhydride (a-3) comprises a compound selected from the group consisting of the following formula (11) to formula (19); [Chemistry 11] (In formula (14), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond or a divalent linking group represented by the following formula (20)); [Chemistry 12] 4 . The resin composition according to claim 1 , further comprising a photohardening initiator (C).

5. A cured product comprising the resin composition according to any one of claims 1 to 3. 6 . A semiconductor element comprising a surface protection film, an interlayer insulating film, or an insulating film for a redistribution layer comprising the resin composition according to claim 1 .

7. A dry film resist, which is obtained by sandwiching the resin composition according to any one of claims 1 to 3 between substrates.

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