Cured resin composition and its cured product

Abstract

A curable resin composition comprising a maleimide resin (A) having a cyclic imide bond and obtained by reacting a diamine (a-1) derived from a dimer acid, a tetracarboxylic dianhydride (a-2), and maleic anhydride, a maleimide resin (B) represented by formula (1), and a curing accelerator (D), the components (A), (B), and (D) being compatible with each other. (In formula (1), the R moieties each independently represent a hydrogen atom or a C1-C5 alkyl group, m is an integer of 0-3, and n, indicating the number of repetitions, is 1<n<5 on average.)

Description

[Technical Field]

[0001] This invention relates to a cured resin composition and its cured product. The curable resin composition of the present invention can be applied to protective films, interlayer insulating films, redistribution layer insulating films, and underfills that can be used in semiconductor devices and semiconductor substrates. [Background technology]

[0002] In recent years, the required characteristics of laminates used to mount electrical and electronic components have become broader and more sophisticated due to the expansion of their application fields. For example, while semiconductor chips were traditionally mounted on metal lead frames, high-performance semiconductor chips such as CPUs are increasingly mounted on laminates made of polymer materials. As the speed of CPUs and other components increases and clock frequencies rise, signal propagation delay and transmission loss become problems, requiring low dielectric constant and low dielectric loss tangent in the wiring boards. At the same time, as the speed of components increases, the heat generated by the chips also increases, creating a need for improved heat resistance. Furthermore, with the recent proliferation of mobile electronic devices such as cell phones, precision electronic equipment is being used and carried in outdoor environments and in close proximity to the human body, requiring resistance to external environments (especially humid and hot environments). Moreover, in the automotive sector, where electronification is rapidly progressing, precision electronic equipment is sometimes placed near the engine, requiring even higher levels of heat and humidity resistance.

[0003] Wiring boards using BT resin, a resin containing a bisphenol A type cyanate ester compound and a bismaleimide compound as disclosed in Patent Document 1, have excellent heat resistance, chemical resistance, and electrical properties, and have been widely used as high-performance wiring boards. However, as described above, improvements are needed in situations where even higher performance is required.

[0004] In this context, maleimide compounds available on the market are often low-molecular-weight and rigid bismaleimide compounds, and because they are crystalline with high melting points, they need to be used in solution form. However, these have drawbacks such as being poorly soluble in common organic solvents and only soluble in high-boiling, highly hygroscopic solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. Furthermore, while cured bismaleimide compounds have good heat resistance, they have the disadvantages of being brittle and highly hygroscopic.

[0005] In response to this, maleimide resins have been developed that have a molecular weight distribution, a relatively low softening point, and better solvent solubility than conventional bismaleimide compounds, as described in Patent Documents 2 and 3. However, they are still not sufficient because there are challenges in their adhesion to substrates in high-temperature environments, particularly to materials such as silicon and copper used as materials for devices and substrates. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japan Special Publication No. 54-30440 [Patent Document 2] Japanese Patent Publication No. 3-100016 [Patent Document 3] Japanese Patent No. 5030297 [Patent Document 4] Japanese Patent No. 6689475 [Patent Document 5] Japan Special Publication No. 4-75222 [Patent Document 6] Japanese Patent No. 6752390 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Generally, when trying to improve the Tg of a resin composition for the purpose of enhancing heat resistance, resins having a ring structure are often used. In this case, however, as the ring structure in the molecule increases, the solubility in solvents tends to decrease. Also, the compatibility between resins decreases, and even if they are maleimide resins, they are not necessarily compatible. In particular, combinations that are incompatible are more common, especially for resins having a plurality of long-chain aliphatic chains and ring structures. A cured product composed of a resin composition using incompatible resins has inferior heat resistance and can cause cracks, so it was unsuitable for use in applications such as protective films, interlayer insulating films, insulating films for rewiring layers, and underfills used in semiconductor elements and semiconductor substrates.

[0008] The present invention has been made in view of such circumstances, and relates to a resin composition containing maleimide resins that are compatible even when the main skeletons are different from each other, and aims to provide a curable resin composition exhibiting excellent heat resistance, mechanical properties, and low dielectric properties, and a cured product thereof. By using two or more maleimide resins that are compatible even when the main skeletons are different from each other, while taking advantage of the merits based on each parent skeleton, that is, properties such as flexibility due to the long-chain skeleton and high heat resistance due to having a plurality of cyclic structures, a cured product excellent in mechanical properties and low dielectric properties can be obtained.

[0009] Furthermore, a resin composition that is stable and has excellent compatibility even in a solution state improves the workability during the production of the resin composition and can mix a variety of other materials, thus broadening the scope of material design.

Means for Solving the Problems

[0010] As a result of intensive research to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the following [1] to

[15] . [1] A maleimide resin (A) having a cyclic imide bond obtained by reacting a diamine (a-1) derived from dimer acid, a tetracarboxylic dianhydride (a-2), and maleic anhydride, and Maleimide resin (B) represented by the following formula (1), Hardening accelerator (D), A curable resin composition comprising components (A), (B), and (D), wherein components (A), (B), and (D) are compatible.

[0011] [ka]

[0012] (In formula (1), each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value is 1) <n<5である。) [2] The curable resin composition according to the preceding paragraph [1], wherein the component (A) is represented by the following formula (2).

[0013] [ka]

[0014] (In formula (2), R 1 This indicates a divalent hydrocarbon group (a) derived from dimer acid, and R 2 This represents a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, and R 3 R represents one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, 4 and R 5 R includes one or more organic groups selected from: a tetravalent organic group having 6 to 40 carbon atoms and independently having a monocyclic or condensed polycyclic alicyclic structure; a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a cross-linking structure; and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure that has both an alicyclic structure and an aromatic ring. 4 and R 5It contains 5 to 95 mol% when the total amount is 100 mol%. m is an integer from 1 to 30, n is an integer from 0 to 30, and when m is 2 or more, there are a plurality of R 1 and R 4 may be the same or different from each other, and when n is 2 or more, there are a plurality of R 2 and R 5 may be the same or different from each other. ) [3] The curable resin composition according to the previous item [1] or [2], wherein the component (a-2) is represented by the following formula (3-a).

[0015]

Chemical formula

[0016] (In formula (3-a), R 6 is a tetravalent organic group having 4 to 40 carbon atoms containing a hydrocarbon ring, and the organic group may contain an aromatic ring. ) [4] The curable resin composition according to the previous item [3], wherein the component (a-2) is selected from the group consisting of the following formulas (4-1a) to (4-11a). [[ID=3z]]

[0017]

Chemical formula

[0018] (In formula (4-4a), X1 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a divalent organic group having 1 to 3 carbon atoms. In formula (4-6a), X2 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms or an arylene group. ) [5] The curable resin composition according to any one of the previous items [1] to [4], further comprising a thermosetting resin (C) other than the components (A) and (B), and the components (A) to (D) being compatible with each other. [6] The curable resin composition according to the preceding paragraph [5], wherein component (C) is one or more selected from the group consisting of maleimide compounds other than component (A) and component (B), cyanate ester compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group. [7] The curable resin composition according to paragraph [5] or [6] above, wherein the component (C) is a compound represented by the following formula (5).

[0019] [ka]

[0020] (In formula (5), R a , R b Each of these is independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 1 to 16 carbon atoms. Na represents a number from 1 to 16, and nb represents a number from 1 to 16. Na and nb may be the same or different. [8] A curable resin composition according to any one of the preceding paragraphs [1] to [7], wherein the component (a-2) is a compound represented by the following formula (6).

[0021] [ka]

[0022] [9] A curable resin composition according to any one of the preceding paragraphs [1] to [7], wherein the component (a-2) is a compound represented by the following formula (7).

[0023] [ka]

[0024]

[10] The curable resin composition according to any one of the preceding paragraphs [1] to [9], wherein component (D) comprises at least one selected from a thermal radical polymerization initiator and an imidazole compound.

[11] The curable resin composition according to the preceding paragraph

[10] , wherein the thermal radical polymerization initiator is an organic peroxide.

[12] A curable resin composition according to any one of the preceding paragraphs [1] to

[11] , wherein the content of component (A) is 30% by weight or more and less than 95% by weight, and the content of component (B) is 3% by weight or more and less than 60% by weight, and the content of component (A) is greater than that of component (B).

[13] A curable resin composition according to any one of the preceding items [1] to

[12] , wherein the haze value at an optical path length of 10 mm, as measured in accordance with JIS K7136, is less than 50.

[14] A resin sheet containing the curable resin composition described in any one of the preceding paragraphs [1] to

[13] .

[15] A cured product obtained by curing any one of the curable resin compositions described in the preceding paragraphs [1] to

[13] .

[16] A semiconductor element and a semiconductor substrate comprising the cured product described in the preceding paragraph

[15] as at least one selected from the group consisting of a surface protective film, an interlayer insulating film, an insulating film for a redistribution layer, and an underfill. [Effects of the Invention]

[0025] The curable resin composition of the present invention exhibits excellent solution stability and compatibility, significantly improving workability, and its cured product also possesses excellent mechanical properties and low dielectric properties. [Modes for carrying out the invention]

[0026] The present invention will be described in detail below. First, the method for producing the maleimide resin of the present invention will be described.

[0027] The maleimide resin (A) of the present invention has a divalent hydrocarbon group (a) derived from a dimer acid and a cyclic imide bond. Such a maleimide resin (A) can be obtained by reacting a diamine (a-1) derived from a dimer acid with a tetracarboxylic dianhydride (a-2) and a maleic anhydride.

[0028] The divalent hydrocarbon group (a) derived from the dimer acid refers to a divalent residue obtained by removing two carboxyl groups from a dicarboxylic acid contained in the dimer acid. In the present invention, such a divalent hydrocarbon group (a) derived from the dimer acid can be introduced into a maleimide resin by reacting a diamine (a-1), obtained by substituting the two carboxyl groups of the dicarboxylic acid contained in the dimer acid with amino groups, with a tetracarboxylic dianhydride (a-2) and maleic anhydride described later to form an imide bond.

[0029] In the present invention, the dimer acid is preferably a dicarboxylic acid having 20 to 60 carbon atoms. Specific examples of the dimer acid include those obtained by dimerizing the unsaturated bonds of unsaturated carboxylic acids such as linoleic acid, oleic acid, and linolenic acid, and then purifying them by distillation. The dimer acid in the above specific example mainly contains a dicarboxylic acid with 36 carbon atoms, and usually contains tricarboxylic acids and monocarboxylic acids with 54 carbon atoms, each up to a maximum of about 5% by mass. The diamine (a-1) derived from the dimer acid of the present invention (hereinafter, sometimes referred to as dimer acid-derived diamine (a-1)) is a diamine obtained by substituting the two carboxyl groups of each dicarboxylic acid contained in the dimer acid with amino groups, and is usually a mixture. In the present invention, such dimer acid-derived diamines (a-1) include, for example, diamines such as [3,4-bis(1-aminoheptyl)6-hexyl-5-(1-octenyl)]cyclohexane, and diamines in which the unsaturated bonds have been saturated by further hydrogenation of these diamines.

[0030] The divalent hydrocarbon group (a) derived from the dimer acid of the present invention, which is introduced into the maleimide resin using such a dimer acid-derived diamine (a-1), is preferably a residue obtained by removing two amino groups from the diamine (a-1) derived from the dimer acid. Furthermore, when obtaining the maleimide resin (A) of the present invention using the diamine (a-1) derived from the dimer acid, one type of diamine (a-1) derived from the dimer acid may be used alone, or two or more types with different compositions may be used in combination. In addition, as such a diamine (a-1) derived from the dimer acid, commercially available products such as "PRIAMINE1074" (manufactured by Croda Japan Co., Ltd.) may be used.

[0031] In the present invention, tetracarboxylic dianhydride (a-2) is a tetracarboxylic dianhydride having an alicyclic structure adjacent to the anhydride group, and having a structure such that when a bismaleimide compound is formed after the reaction, the portion adjacent to the imide ring becomes an alicyclic structure. In addition to having an alicyclic structure in the portion adjacent to the imide ring, the structure may also contain aromatic rings.

[0032] In the present invention, the maleimide resin (A) is preferably of the following formula (2). In formula (2), R 4 and R 5 This structure is derived from tetracarboxylic dianhydride (a-2).

[0033] [ka]

[0034] (In formula (2), R 1 This represents a divalent hydrocarbon group (a) derived from dimer acid, and R 2 This represents a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, and R 3 R represents one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, 4 and R5 This represents one or more organic groups selected from: a tetravalent organic group having 4 to 40 carbon atoms (preferably 6 to 40 carbon atoms) having a monocyclic or condensed polycyclic alicyclic structure independently; a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a cross-linking structure; and a tetravalent organic group having 8 to 40 carbon atoms having a semi-alicyclic structure possessing both an alicyclic structure and an aromatic ring. m is an integer from 1 to 30, n is an integer from 0 to 30, and R 4 and R 5 (These may be the same or different.)

[0035] In the present invention, the tetracarboxylic dianhydride (a-2) is preferably a tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the following formula (3). The tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the following formula (3) has an alicyclic structure adjacent to the anhydride group.

[0036] [ka]

[0037] (In formula (3), Cy is a tetravalent organic group having 4 to 40 carbon atoms and containing a hydrocarbon ring, and this organic group may also contain an aromatic ring.)

[0038] The tetracarboxylic dianhydride (a-2) having the alicyclic structure shown in formula (3) above can be specifically represented by the following formula (3-a). [ka] (In formula (3-a), R 6 This refers to a tetravalent organic group having 4 to 40 carbon atoms and containing a hydrocarbon ring; this organic group may also contain an aromatic ring.

[0039] In the present invention, the tetracarboxylic dianhydride (a-2) is preferably a tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the following formulas (4-1) to (4-11). The tetracarboxylic dianhydride (a-2) represented by formulas (4-1) to (4-11) has a structure comprising a tetravalent organic group having 4 to 40 carbon atoms (preferably 6 to 40 carbon atoms) having a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a cross-linking structure, or a tetravalent organic group having 8 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring.

[0040] [ka]

[0041] (In formula (4-4), X1 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms. In formula (4-6), X2 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms or an arylene group.)

[0042] The tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the above formulas (4-1) to (4-11) can specifically be expressed as the following formulas (4-1a) to (4-11a).

[0043] [ka]

[0044] (In formula (4-4a), X1 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms. In formula (4-6a), X2 is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or an arylene group.)

[0045] The tetracarboxylic dianhydride (a-2) used in the present invention has a tetravalent organic group having 4 to 40 carbon atoms (preferably 6 to 40 carbon atoms) having a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a cross-linking structure, or a tetravalent organic group having 8 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. Examples of tetracarboxylic dianhydrides having an alicyclic structure (a-2) include, specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic-3,4:3',4'-dianhydride (H-BPDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2, Examples include alicyclic tetracarboxylic dianhydrides such as 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norbornaneacetic acid dianhydride, or compounds in which these aromatic rings are substituted with alkyl or halogen atoms; and semi-alicyclic tetracarboxylic dianhydrides such as 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, or compounds in which hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms.

[0046] In the present invention, the tetracarboxylic dianhydride (a-2) is preferably a tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the following formula (6).

[0047] [ka]

[0048] In the present invention, the tetracarboxylic dianhydride (a-2) is preferably a tetracarboxylic dianhydride (a-2) having an alicyclic structure represented by the following formula (7).

[0049] [ka]

[0050] In the present invention, in addition to tetracarboxylic dianhydride (a-2) having an alicyclic structure, acid dianhydride without an alicyclic structure or acid dianhydride containing an aromatic ring adjacent to the anhydride group may also be added. The lower limit of tetracarboxylic dianhydride (a-2) in the total amount of acid dianhydride is preferably 40 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The upper limit may be 100 mol% or less. If the content of tetracarboxylic dianhydride (a-2) in the total amount of acid dianhydride is less than 40 mol%, the light-gathering efficiency tends to be low, and small pattern apertures cannot be obtained, which may reduce the resolution of the resulting pattern.

[0051] Other acid dianhydrides containing an aromatic ring adjacent to the anhydride group, other than the aforementioned tetracarboxylic dianhydride (a-2), include pyromellitic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, and 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride. Examples of aromatic acid dianhydrides include anhydrides, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or compounds in which the aromatic ring of these compounds is substituted with alkyl or halogen atoms, and acid dianhydrides having an amide group. These can be used in combination of two or more acid dianhydrides containing an alicyclic or semi-alicyclic structure with 4 to 40 carbon atoms.

[0052] Furthermore, the maleimide resin (A) may be a bismaleimide compound obtained by reacting the dimer acid-derived diamine (a-1), an organic diamine other than the dimer acid-derived diamine (a-1) (a-3), the tetracarboxylic dianhydride (a-2), and the maleic anhydride. By copolymerizing the organic diamine other than the dimer acid-derived diamine (a-1) (a-3), it becomes possible to control the required physical properties as needed, such as further reducing the tensile modulus of the resulting cured product.

[0053] Organic diamines (a-3) other than the diamine (a-1) derived from the dimer acid (hereinafter, sometimes simply referred to as organic diamine (a-3)) refer to diamines other than the diamine (a-1) derived from the dimer acid in the present invention. Such organic diamines (a-3) are not particularly limited and include, for example, aliphatic diamines such as 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane; 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, and 1,3-bis(4-aminophenoxy)benzene. Examples include aromatic diamines such as zen, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, and 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylsulfone; 3,3'-diaminodiphenylsulfone; 4,4'-diaminobenzophenone; 4,4'-diaminodiphenyl sulfide; and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Among these, from the viewpoint of obtaining a cured product with a lower tensile modulus, aliphatic diamines having 6 to 12 carbon atoms such as 1,6-hexamethylenediamine; diaminocyclohexanes such as 1,4-diaminocyclohexane; and aromatic diamines having an aliphatic structure with 1 to 4 carbon atoms in the aromatic skeleton such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane are more preferable. Furthermore, when obtaining the maleimide resin (A) of the present invention using these organic diamines (a-3), one of these organic diamines (a-3) may be used alone, or two or more may be used in combination.

[0054] The method of reacting the diamine (a-1) derived from the dimer acid with the alicyclic tetracarboxylic dianhydride (a-2) and the maleic anhydride, or the method of reacting the diamine (a-1) derived from the dimer acid with the organic diamine (a-3) with the alicyclic tetracarboxylic dianhydride (a-2) and the maleic anhydride, is not particularly limited, and any known method can be used as appropriate. For example, first, polyamic acid is synthesized by stirring the diamine derived from the dimer acid (a-1), the tetracarboxylic dianhydride (a-2), and optionally the organic diamine (a-3) in a solvent such as toluene, xylene, tetralin, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or a mixture thereof, at room temperature (around 23°C) for 30 to 60 minutes. Then, maleic anhydride is added to the obtained polyamic acid and stirred at room temperature (around 23°C) for 30 to 60 minutes to synthesize polyamic acid with maleic acid added to both ends. The desired maleimide resin (A) can be obtained by further adding a solvent that forms an azeotrope with water, such as toluene, to this polyamic acid and refluxing at a temperature of 100 to 160°C for 3 to 6 hours while removing the water generated during imidation. In addition, catalysts such as pyridine and methanesulfonic acid may be further added in this method.

[0055] In the above reaction, it is preferable that the mixing ratio of the raw materials be such that (total number of moles of all diamines and organic diamines (a-3) contained in the diamine (a-1) derived from dimer acid) : (total number of moles of tetracarboxylic dianhydride (a-2) having an alicyclic structure + 1 / 2 of the number of moles of maleic anhydride) is 1:1. Furthermore, when using the organic diamine (a-3), from the viewpoint that flexibility derived from dimer acid is expressed and a cured product with a lower modulus of elasticity tends to be obtained, it is preferable that (number of moles of organic diamine (a-3)) / (number of moles of all diamines contained in the diamine (a-1) derived from dimer acid) be 1 or less, and more preferably 0.4 or less. Furthermore, when using the aforementioned organic diamine (a-3), the polymerization of the amidic acid unit consisting of a diamine (a-1) derived from a dimer acid and a tetracarboxylic dianhydride (a-2) having an alicyclic structure, and the amidic acid unit consisting of the organic diamine (a-3) and the tetracarboxylic dianhydride (a-2) having an alicyclic structure, may be random polymerization or block polymerization.

[0056] The maleimide resin (A) obtained in this manner is preferably the maleimide resin (A) represented by the following formula (2).

[0057] [ka]

[0058] (In general formula (2), R 1 This represents a divalent hydrocarbon group (a) derived from dimer acid, and R 2 This represents a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, and R 3 R represents one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than a divalent hydrocarbon group (a) derived from dimer acid, 4 and R 5This represents one or more organic groups selected from: a tetravalent organic group having 4 to 40 carbon atoms (preferably 6 to 40 carbon atoms) having a monocyclic or condensed polycyclic alicyclic structure independently; a tetravalent organic group having 8 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked to each other directly or via a cross-linking structure; and a tetravalent organic group having 8 to 40 carbon atoms having a semi-alicyclic structure possessing both an alicyclic structure and an aromatic ring. m is an integer from 1 to 30, n is an integer from 0 to 30, and R 4 and R 5 (These may be the same or different.)

[0059] The divalent hydrocarbon group (a) derived from the dimer acid in formula (2) is as described above. In the present invention, the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid in formula (2) refers to the divalent residue obtained by removing two amino groups from the organic diamine (a-3). However, in the same compound, the divalent hydrocarbon group (a) derived from the dimer acid and the divalent organic group (b) are not the same. Furthermore, the tetravalent organic group in formula (2) refers to the tetravalent residue obtained by removing two groups represented as -CO-O-CO- from the tetracarboxylic dianhydride.

[0060] In formula (2) above, m is the number of repeating units (hereinafter, sometimes referred to as dimer acid-derived structures) containing a divalent hydrocarbon group (a) derived from the dimer acid, and is an integer from 1 to 30. When the value of m exceeds the upper limit, the solubility in the solvent decreases, and in particular, the solubility in the developer during development, as described later, tends to decrease. Furthermore, from the viewpoint of achieving good solubility in the developer during development, the value of m is particularly preferably between 3 and 10.

[0061] In formula (2) above, n is the number of repeating units containing the divalent organic group (b) (hereinafter, sometimes referred to as the organic diamine-derived structure), and is an integer between 0 and 30. If the value of n exceeds the upper limit, the flexibility of the resulting cured product deteriorates, and it tends to become a hard and brittle resin. Furthermore, from the viewpoint of obtaining a cured product with a low modulus of elasticity, a value of 0 to 10 is particularly preferable for n.

[0062] Furthermore, if m in formula (2) is 2 or more, R 1 and R 4 The elements may be the same or different between each repeating unit. Also, if n in formula (2) is 2 or greater, R 2 and R 5 These may be the same or different between each repeating unit. Furthermore, the bismaleimide compound represented by formula (2) may have the dimer acid-derived structure and the organic diamine-derived structure be random or blocky.

[0063] Furthermore, when obtaining the maleimide compound (A) of the present invention from the diamine (a-1) derived from the dimer acid, the maleic anhydride, the tetracarboxylic dianhydride (a-2), and optionally the organic diamine (a-3), if the reaction rate is 100%, then n and m can be expressed by the mixed molar ratio of the total diamine contained in the diamine (a-1) derived from the dimer acid, the organic diamine (a-3), the maleic anhydride, and the tetracarboxylic dianhydride (a-2). That is, (m+n):(m+n+2) is expressed as (total number of moles of all diamines and organic diamines (a-3) contained in the diamine (a-1) derived from dimer acid):(total number of moles of maleic anhydride and tetracarboxylic dianhydride (a-2)), m:n is expressed as (number of moles of all diamines contained in the diamine (a-1) derived from dimer acid):(number of moles of organic diamine (a-3)), and 2:(m+n) is expressed as (number of moles of maleic anhydride):(number of moles of tetracarboxylic dianhydride (a-2)).

[0064] Furthermore, in the maleimide resin (A), the sum of m and n (m+n) is preferably 2 to 30, from the viewpoint that a cured product with a lower modulus of elasticity tends to be obtained. Also, the ratio of m to n (n / m) is preferably 1 or less, and more preferably 0.4 or less, from the viewpoint that flexibility derived from dimer acid is expressed and a cured product with a lower modulus of elasticity tends to be obtained.

[0065] Maleimide resin (A) may be used alone or in combination of two or more types.

[0066] Next, we will explain the method for producing maleimide resin (B). Maleimide resin (B) can use an aromatic amine resin represented by the following formula (8) as a precursor.

[0067] [ka]

[0068] (In formula (8), each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value is 1) <n<5である。)

[0069] The aromatic amine resin represented by formula (8) is more preferably represented by formula (9) below. This is because the crystallinity is lower compared to when the substitution position of the C1-C5 alkyl group on the benzene ring not bonded to the amino group in formula (8) is at the para position.

[0070] [ka]

[0071] (In formula (9), each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value is 1) <n<5である。)

[0072] The method for producing the aromatic amine resin represented by formula (8) or formula (9) is not particularly limited. For example, when R is a hydrogen atom, aniline is used as described in Patent Document 4, and when R is an alkyl group of 1 to 5, it can be obtained by reacting 2-alkylanilines such as 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-isopropylaniline, 2-butylaniline, 2-tert-butylaniline, and 2-amylaniline with diisopropenylbenzene or di(α-hydroxyisopropyl)benzene in the presence of an acidic catalyst at 180 to 250°C, as described in Patent Document 5.

[0073] When synthesizing the aromatic amine resin represented by formula (8) above, the acidic catalysts used include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, activated clay, ion exchange resins, and other acidic catalysts. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.1 to 50% by weight, preferably 1 to 30% by weight, relative to the aniline used. Too much catalyst will make the reaction solution too viscous and difficult to stir, while too little will slow down the reaction.

[0074] The reaction may be carried out using organic solvents such as toluene and xylene as needed, or without a solvent. For example, after adding an acidic catalyst to a mixed solution of 2-alkylaniline and a solvent, if the catalyst contains water, it is preferable to remove the water from the system by azeotropy. Then, diisopropenylbenzene or di(α-hydroxyisopropyl)benzene is added, and the reaction is carried out at 140-220°C, preferably 160-200°C, for 5-50 hours, preferably 5-30 hours, while removing the solvent from the system. When di(α-hydroxyisopropyl)benzene is used, water is produced as a by-product, so it is removed from the system by azeotropic reaction with the solvent during heating. After the reaction is complete, the acidic catalyst is neutralized with an alkaline aqueous solution, and then a water-insoluble organic solvent is added to the oil layer and the washing is repeated until the wastewater becomes neutral, after which the solvent and excess aniline derivative are removed under heated reduced pressure. If activated clay or ion exchange resin is used, the reaction solution is filtered after the reaction is complete to remove the catalyst.

[0075] Maleimide resin (B) is obtained by adding or dehydrating condensing the aromatic amine resin represented by formula (8) obtained by the above process with maleic acid or maleic anhydride (hereinafter also referred to as "maleic anhydride") in the presence of a solvent and a catalyst.

[0076] Since the water generated during the reaction must be removed from the system, a solvent that is not water-soluble is used in the reaction. Examples include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more solvents may be used in combination.

[0077] Furthermore, an aprotic polar solvent can be used in combination with the aforementioned water-insoluble solvent. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrolidone, and two or more of these may be used in combination. When using an aprotic polar solvent, it is preferable to use one with a higher boiling point than the water-insoluble solvent used in combination.

[0078] Furthermore, the catalyst used in the reaction is an acidic catalyst and is not particularly limited, but examples include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. The amount of acidic catalyst used is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, relative to the aromatic amine resin.

[0079] For example, an aromatic amine resin represented by formula (8) is dissolved in toluene and N-methyl-2-pyrrolidone, maleic anhydride is added to produce amical, and then p-toluenesulfonic acid is added, and the reaction is carried out under reflux conditions while removing the water produced from the system.

[0080] Alternatively, maleic anhydride is dissolved in toluene, and under stirring, an N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by formula (8) is added to produce amitic acid. Then, p-toluenesulfonic acid is added, and the reaction is carried out under reflux conditions while removing the water produced from the system.

[0081] Alternatively, maleic anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and the toluene solution of the aromatic amine resin represented by formula (8) is added dropwise under stirring and reflux conditions, while removing any azeotrope-forming water from the system and returning the toluene to the system as the reaction proceeds (this completes the first stage reaction).

[0082] In either method, maleic anhydride is typically used in an amount of 1 to 3 times the equivalent, preferably 1.2 to 2.0 times, relative to the amino group of the aromatic amine resin represented by formula (8).

[0083] To reduce the amount of unclosed amic acid, after the maleimide reaction listed above, water is added to the reaction solution to separate it into a resin solution layer and an aqueous layer. Excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst are dissolved in the aqueous layer, so these are removed by liquid-liquid extraction, and the same procedure is repeated to thoroughly remove excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst. The catalyst is then added back to the maleimide resin solution in the organic layer from which the excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst have been removed, and the dehydration and ring-closing reaction of the remaining amic acid is carried out again under heated reflux conditions to obtain a maleimide resin solution with a low acid value (the above is the second stage reaction).

[0084] The re-dehydration and ring-closing reaction takes typically 1 to 10 hours, preferably 1 to 5 hours, and the aforementioned aprotic polar solvent may be added as needed. After the reaction is complete, the mixture is cooled and washed with water repeatedly until the water becomes neutral. Then, the water is removed by azeotropic dehydration under reduced pressure, and the solvent may be removed by distillation or another solvent may be added to adjust the resin solution to the desired concentration, or the solvent may be completely removed to obtain the solid resin.

[0085] The maleimide resin (B) obtained by the manufacturing method described above has a structure represented by the following formula (1).

[0086] [ka]

[0087] (In formula (1), each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n is the number of repetitions, and its average value is 1) <n<5である。)

[0088] In formula (1) above, m is usually 0 to 3, preferably 0 to 2, and more preferably 0. R 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. If m is greater than 3 or R is an alkyl group having 6 or more carbon atoms, the electrical properties may deteriorate due to molecular vibrations when the alkyl group is exposed to high frequency.

[0089] In equation (1), the value of n can be calculated from the number-average molecular weight obtained by gel permeation chromatography (GPC, detector: RI) of the maleimide resin (B), but it can be considered to be approximately equivalent to the value of n calculated from the GPC measurement results of the aromatic amine resin represented by equation (8) above, which is the raw material.

[0090] The content of the n=1 component in equation (1) can be determined by gel permeation chromatography (GPC, detector: RI) analysis.

[0091] In formula (1) above, when n=1, the solubility in the solvent is low, and when n is 5 or more, the flowability during molding deteriorates, and the properties of the cured product cannot be fully exhibited.

[0092] The maleimide resin (B) preferably has a molecular weight distribution, and the content of n=1 in formula (1) by GPC analysis (RI) is preferably 98 area% or less, more preferably 20 to 98 area%, even more preferably 30 to 95 area%, and particularly preferably 50 to 90 area%. When the content of n=1 is 98 area% or less, the heat resistance is good and the solubility is also improved. On the other hand, the lower limit of n=1 may be 0 area%, but when it is 30 area% or more, the viscosity of the resin solution decreases and the impregnation is good.

[0093] The softening point of maleimide resin (B) is preferably 50°C to 150°C, more preferably 80°C to 120°C, even more preferably 90°C to 110°C, and particularly preferably 95°C to 105°C. The melt viscosity at 150°C is 0.05 to 100 Pa·s, preferably 0.1 to 40 Pa·s.

[0094] Maleimide resin (B) is more preferably a structure represented by formula (10). This is because when R in formula (1) is an alkyl group having 1 to 5 carbon atoms, the crystallinity decreases compared to when the substitution position of the propyl group on the benzene ring to which the maleimide group is not bonded is at the para position.

[0095] [ka]

[0096] (In formula (10), each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value is 1) <n<5である。)

[0097] The preferred ranges for R and m in formula (10) are the same as those in formula (1).

[0098] The content of maleimide resin (A) is preferably 30% to less than 95% by weight of the total amount of the curable resin composition, more preferably 40% to less than 90% by weight, and even more preferably 50% to less than 90% by weight. The content of maleimide resin (B) is preferably 3% to less than 60% by weight of the total amount of the curable resin composition, more preferably 5% to less than 50% by weight, and even more preferably 10% to less than 40% by weight. It is also desirable that the content of maleimide resin (A) is greater than that of maleimide resin (B). In the above ranges, the cured product tends to have high mechanical strength, high peel strength, and good heat resistance while maintaining flexibility. Note that the amount of solvent is not included in the total amount of the curable resin composition.

[0099] Maleimide resin (A) and maleimide resin (B) are characterized by their excellent compatibility. In this application, "compatible" means that when a curable resin composition is formed by uniformly mixing two or more resins, the haze of the solution is less than 50 in the case of a liquid, and when a cured product is formed, only one glass transition temperature (Tg) is measured for the curable resin composition. In other words, when the resins are "not compatible," the haze is 50 or more in the case of a liquid, and in the case of a cured product, multiple Tg values ​​are measured even if the resins are uniformly mixed.

[0100] The compatibility and haze of the curable resin composition of the present invention were measured as follows. [compatibility] When curable resin compositions were visually observed, those without precipitates or other defects and that could be applied to a substrate were classified as having good compatibility, while those with precipitates or other defects that made application to a substrate difficult were classified as having poor compatibility. [Haze value] In accordance with JIS K7136, the curable resin composition was placed in a square cell with a path length of 10 mm, and light was irradiated onto the curable resin composition using a color and turbidity simultaneous measuring instrument (Nippon Denshoku, COH400) at 25°C. The total light transmittance (Tt), which represents the total amount of light transmitted, and the diffuse light transmittance (Td), which is transmitted after being diffused by the sheet, were calculated using the following formula (1). The total light transmittance (Tt) is the sum of the parallel light transmittance (Tp) and the diffuse light transmittance (Td) that are transmitted while remaining coaxial with the incident light. Hayes (H) = Td / Tt × 100 ... (1)

[0101] The curable resin composition of the present invention may contain a thermosetting resin (C) as a thermosetting component other than the maleimide resins (A) and (B) of the present invention.

[0102] When thermosetting resin (C) is incorporated, the amount is not particularly limited, but is preferably 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times.

[0103] The thermosetting resin (C) is not particularly limited as long as it is a compound having a functional group (or structure) that can crosslink with the maleimide resin, such as an amino group, cyanate group, phenolic hydroxyl group, alcoholic hydroxyl group, allyl group, methallyl group, acrylic group, methacrylic group, vinyl group, or conjugated diene group. Specifically, examples include amine compounds, cyanate ester compounds, epoxy resins, phenolic resins, oxetane resins, carbodiimide compounds, benzoxazine compounds, compounds having ethylenically unsaturated groups, and compounds having acid anhydride groups. In addition, maleimide compounds other than the maleimide resins (A) and (B) of the present invention may be used in combination.

[0104] Conventionally known amine compounds can be used as amine compounds that can be incorporated into the curable resin composition of the present invention. Specific examples of amine compounds include, but are not limited to, the aromatic amine resin represented by formula (8), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, polyoxypropylenediamine, polyoxypropylenetriamine, N-aminoethylpiperazine, and aniline-formaldehyde resin. These may be used individually or in combination of two or more. Furthermore, the aromatic amine resin described in the claims of Patent Document 3 is particularly preferred because it has excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0105] When incorporating an amine compound, the amount is not particularly limited, but is preferably 0.1 to 10 times the weight ratio of maleimide resins (A) and (B), and more preferably in the range of 0.2 to 4 times.

[0106] Other maleimide compounds besides the maleimide resins (A) and (B) that can be incorporated into the curable resin composition of the present invention can be conventionally known maleimide compounds. Specific examples of maleimide compounds are not particularly limited, as long as they are compounds having one or more maleimide groups in their molecules. Specific examples include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimoidhexanoic acid, 4-maleimoidbutyric acid, bis(4-maleimoidphenyl)methane, 2,2-bis{4-(4-maleimoidphenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-diphenylmethane) (Tyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimide) Phenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1,6-bismaleimidehexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane n, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,Examples include 5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, polyphenylmethanemaleimide, maleimide compounds represented by the following formula (5), maleimide compounds represented by the following formula (11), maleimide compounds represented by the following formula (12), maleimide compounds represented by the following formula (13), maleimide compounds represented by the following formula (14), and other maleimide compounds represented by the following formula (15), maleimide compounds represented by the following formula (16), maleimide compounds represented by the following formula (17), maleimide compounds represented by the following formula (18), maleimide compounds represented by the following formula (19), and fluorescein-5-maleimide, as well as prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These other maleimide compounds can also be used individually or in appropriate combinations of two or more.

[0107] [ka]

[0108] (In formula (5), R a , R b Each of these is independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 1 to 16 carbon atoms. Na represents a number from 1 to 16, and nb represents a number from 1 to 16. Na and nb may be the same or different.

[0109] In equation (5) above, R a , R bEach of these is independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 1 to 16 carbon atoms. Linear or branched alkyl groups are preferred, and linear alkyl groups are more preferred because they can lower dielectric properties. The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 4 to 12. The number of carbon atoms in the alkenyl group is preferably 1 to 16, and more preferably 4 to 12.

[0110] The alkyl group in formula (5) is preferably an n-heptyl group, an n-octyl group, or an n-nonyl group, with the n-octyl group being more preferred, as it exhibits excellent photocurability. The alkenyl group is preferably a 2-heptenyl group, a 2-octenyl group, or a 2-nonenyl group, with the 2-octenyl group being more preferred.

[0111] In formula (5) above, na is 1 or more, preferably 2 to 16, and more preferably 3 to 14. nb is 1 or more, preferably 2 to 16, and more preferably 3 to 14. na and nb may be the same or different.

[0112] [ka]

[0113] In formula (11), each of the multiple R1s independently represents a hydrogen atom or a methyl group. n represents an integer of 1 or more, preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0114] [ka]

[0115] In formula (12), R2 independently represents a hydrogen atom, a C1-C5 alkyl group, or a phenyl group; l independently represents an integer from 1 to 3; and n represents an integer from 1 to 10. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and neopentyl groups.

[0116] [ka]

[0117] In formula (13), n is 1 or greater, preferably 1 to 21, and more preferably 1 to 16.

[0118] [ka]

[0119] In equation (14), the values ​​of x range from 10 to 35, and the values ​​of y range from 10 to 35.

[0120] [ka]

[0121] In equation (15), n represents an integer between 1 and 10, and m² represents an integer between 8 and 40.

[0122] [ka]

[0123] In equation (16), n6 represents an integer between 1 and 10, and m3 represents an integer between 8 and 40.

[0124] [ka]

[0125] In equation (17), n represents an integer greater than or equal to 1, preferably an integer between 1 and 10.

[0126] [ka]

[0127] [ka]

[0128] In formula (19), R3 independently represents a hydrogen atom, a methyl group, or an ethyl group, and R4 independently represents a hydrogen atom or a methyl group.

[0129] Other maleimide compounds can also be obtained from commercially available products. An example of a maleimide compound represented by formula (5) is BMI-689 (trade name) manufactured by DESIGNER MOLECURES Inc. An example of a maleimide compound represented by formula (11) is BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. An example of a maleimide compound represented by formula (12) is MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. Examples of maleimide compounds represented by formula (13) include BMI-1000P (trade name, n=13.6 (average) in formula (13)) manufactured by K.I. Chemicals Co., Ltd., BMI-650P (trade name, n=8.8 (average) in formula (13)) manufactured by K.I. Chemicals Co., Ltd., BMI-250P (trade name, n=3 to 8 (average) in formula (13)) manufactured by K.I. Chemicals Co., Ltd., and CUA-4 (trade name, n=1 in formula (13)) manufactured by K.I. Chemicals Co., Ltd. Examples of maleimide compounds represented by formula (14) include BMI-6100 (trade name, x=18, y=18 in formula (14)) manufactured by Designer Molecules Inc. Examples of maleimide compounds represented by formula (15) include BMI-1500 (trade name, n=1.3 in formula (15), functional group equivalent: 754 g / eq.) manufactured by Designer Molecules Inc. As the maleimide compound represented by formula (16), commercially available products can be used, for example, BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI). Commercially available maleimide compounds represented by formula (17) can also be used, such as BMI-3000 (trade name), BMI-5000 (trade name), and BMI-9000 (trade name) manufactured by Designer Molecules Inc. (DMI). As the maleimide compound represented by formula (18), commercially available products can also be used, for example, BMI-TMH (trade name) manufactured by Yamato Chemical Industries, Ltd. As the maleimide compound represented by formula (19), commercially available products can be used, for example, BMI-70 (trade name) manufactured by K.I. Chemicals Co., Ltd. These other maleimide compounds can also be used individually or in appropriate combinations of two or more.

[0130] In the curable resin composition of the present invention, the total content of the above-mentioned other maleimide compounds is not particularly limited, but from the viewpoint of obtaining better adhesion to chips and substrates, etc., it is preferably 0.01 to 95 parts by mass, more preferably 0.1 to 90 parts by mass, even more preferably 5 to 80 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of resin solids in the curable resin composition of the present invention.

[0131] Conventional known cyanate ester compounds can be used as the cyanate ester compounds that can be incorporated into the curable resin composition of the present invention. Specific examples of cyanate ester compounds include, but are not limited to, cyanate ester compounds obtained by reacting polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensates of bisphenols and various aldehydes with cyanide halides. These may be used individually or in combination of two or more. Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene. Examples of the above-mentioned aldehydes include formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde. Examples of the above-mentioned diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene. Examples of the above-mentioned ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone. Furthermore, the cyanate ester compounds whose synthesis method is described in Japanese Patent Application Publication No. 2005-264154 are particularly preferred as cyanate ester compounds because they have excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0132] Specific examples of cyanate ester compounds that can be incorporated into the curable resin composition of the present invention include cyanatobenzene, 1-cyanato-2-,1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato-2-,1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-,1-cyanato-2,4-,1-cyanato-2,5-,1-cyanato-2,6-,1-cyanato-3,4-, or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanato Tononylbenzene, 2-(4-cyanaphenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl(4-cyanatophenyl (L) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatomethyl ester, 4-cyanatophenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene n, 1,4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methoxynaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl)propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2,2-bis(4-cyanatophenyl)hexap Luoropropane, 2,2-bis(4-cyanato-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanatophenyl)butane, 1,1-bis(4-cyanatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl)-3-methylbutane, 1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane, 2,2 -Bis(4-cyanatophenyl)hexane, 2,2-bis(4-cyanatophenyl)-3-methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl) Anatophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanatophenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2-methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanatophenyl)phenylmethane, 1,1-Bis(4-cyanatophenyl)-1-phenylethane, bis(4-cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis(4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl ]benzene, 1,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4 -Cyanatobenzoate), bis-(4-cyanatophenyl) carbonate, 1,3-bis(4-cyanatophenyl) adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyl adamantane, 3,3-bis(4-cyanatophenyl) isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl) isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanatophenyl) fluorene, 9,9-bis(4-cyanato- 3-methylphenyl)fluorene, 9,9-bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane, 1,1,1-tris(4-cyanatophenyl)ethane, 1,1,3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-Bis(N-methyl-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, Tris(3, Examples include 5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1-methyl-3,3-bis(4-cyanatophenyl)indorin-2-one, and 2-phenyl-3,3-bis(4-cyanatophenyl)indorin-2-one.

[0133] When a cyanate ester compound is incorporated, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of cyanate ester compound is in the range of 0.1 to 10 times, the heat resistance and dielectric properties of the cured product are excellent.

[0134] In the curable resin composition of the present invention, an epoxy resin may be further blended. Any conventionally known epoxy resin can be used as the blended epoxy resin. Specific examples of epoxy resins include, but are not limited to, glycidyl ether epoxy resins obtained by glycidylating polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, polycondensates of bisphenols and various aldehydes, and alcohols; alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate; glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol; and glycidyl ester epoxy resins. These may be used individually or in combination of two or more. Furthermore, epoxy resins obtained by using phenol aralkyl resins, which are produced by condensing phenols with bishalogenomethylaralkyl derivatives or aralkyl alcohol derivatives, as raw materials and then dehydrochlorinating them with epichlorohydrin are particularly preferred as epoxy resins because they exhibit excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0135] When epoxy resin is incorporated, the amount is not particularly limited, but it is preferably 0.1 to 10 times the weight of the maleimide resin, and more preferably in the range of 0.2 to 4 times. When the amount of epoxy resin is in the range of 0.1 to 10 times, the strength and dielectric properties of the cured product are excellent.

[0136] In the curable resin composition of the present invention, a compound having a phenolic resin may be further incorporated. Any conventionally known phenolic resin can be used as the phenolic resin that can be incorporated. Specific examples of phenolic resins include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbone). Examples include polymers of lunadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.; polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.); polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of bisphenols and various aldehydes; and modified products thereof. These may be used individually or in combination of two or more. Furthermore, phenol aralkyl resins obtained by condensing phenols with the aforementioned bishalogenomethyl aralkyl derivatives or aralkyl alcohol derivatives are particularly preferred as phenol resins because they exhibit excellent low hygroscopicity, flame retardancy, and dielectric properties.Furthermore, if the phenolic resin has allyl or metharyl groups, it is preferable because its reactivity with maleimide groups is better than that of hydroxyl groups, resulting in a faster curing rate and increased crosslinking points, thus improving strength and heat resistance. Additionally, allyl ethers or metharyl ethers of the phenolic resin, in which the hydroxyl groups have been allylated, can also be incorporated, and because the hydroxyl groups are etherified, the water absorption is reduced.

[0137] When incorporating phenolic resin, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of phenolic resin is in the range of 0.1 to 10 times, the adhesive strength and dielectric properties of the cured product are excellent.

[0138] Generally known oxetane resins can be used as the oxetane resins that can be incorporated into the curable resin composition of the present invention. Examples include, but are not particularly limited, oxetane, alkyl oxetanes such as 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 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). These oxetane resins can be used individually or in appropriate mixtures of two or more types.

[0139] When oxetane resin is incorporated, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of oxetane resin is in the range of 0.1 to 10 times, the adhesive strength and dielectric properties of the cured product are excellent.

[0140] The carbodiimide compounds that can be incorporated into the curable resin composition of the present invention are not particularly limited as long as they have at least one carbodiimide group in their molecule, and generally known compounds can be used. Examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, cycliccarbodiimide, Carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.), and polycarbodiimides such as Stavaxol (registered trademark: manufactured by LANXESS Deutschland GmbH). These carbodiimide compounds can be used individually or in appropriate mixtures of two or more.

[0141] When a carbodiimide compound is incorporated, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of the carbodiimide compound is in the range of 0.1 to 10 times, the adhesive strength and dielectric properties of the cured product are excellent.

[0142] As benzoxazine compounds that can be incorporated into the curable resin composition of the present invention, any compound having two or more dihydrobenzoxazine rings in one molecule can be used, and any generally known compound can be used. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein type benzoxazine, etc. are examples, but are not particularly limited. These benzoxazine compounds can be used individually or in appropriate mixtures of two or more.

[0143] When a benzoxazine compound is incorporated, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of the benzoxazine compound is in the range of 0.1 to 10 times, the adhesive strength and dielectric properties of the cured product are excellent.

[0144] The compounds having ethylenically unsaturated groups that can be incorporated into the curable resin composition of the present invention are not particularly limited, as long as they have one or more ethylenically unsaturated groups in one molecule, and generally known compounds can be used. Examples include compounds having (meth)acryloyl groups and vinyl groups.

[0145] When a compound having an ethylenically unsaturated group is incorporated, the amount is not particularly limited, but preferably it is 0.1 to 10 times the total amount of maleimide resins (A) and (B) by weight, and more preferably in the range of 0.2 to 4 times. When the amount of the compound having an ethylenically unsaturated group is in the range of 0.1 to 10 times, the adhesive strength and dielectric properties of the cured product are excellent.

[0146] Compounds containing a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (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, diethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, and polypropylene glycol di(meth)acrylate. Examples include epoxy di(meth)acrylate adipic acid, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid neopeneglycol 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 their ethylene oxide adducts; pentaerythritol tri(meth)acrylate, and its ethylene oxide adducts; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and their ethylene oxide adducts.

[0147] Other examples include urethane (meth)acrylates that possess both a (meth)acryloyl group and a urethane bond within the same molecule; polyester (meth)acrylates that possess both a (meth)acryloyl group and an ester bond within the same molecule; epoxy (meth)acrylates derived from epoxy resins that also possess a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0148] Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates with polyisocyanates and other alcohols used as needed. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; glycerin (meth)acrylates such as glycerin mono(meth)acrylate and glycerin di(meth)acrylate; pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa( Examples of urethane (meth)acrylates include those obtained by reacting sugar alcohols (meth)acrylates such as meth)acrylate with toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and biuret reaction products.

[0149] 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 phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; di(poly)ester (meth)acrylates such as hydroxypivalate ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalate ester 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 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of trimethylolpropane or glycerin.

[0150] Examples include mono, di, tri, or tetra(meth)acrylate triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono or poly(meth)acrylate triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of dipentaerythritol; and mono(meth)acrylate or poly(meth)acrylate triols of polyhydric alcohols such as tetraol, pentaol, or hexaol.

[0151] 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, sebatic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and their anhydrides; and polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols consisting of the aforementioned diol components, polybasic acids, and their anhydrides, as well as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc.

[0152] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadienephenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and acid anhydride-modified epoxy (meth)acrylates thereof.

[0153] Examples of compounds containing a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, ethylstyrene, and divinylbenzene. Other vinyl compounds include triallyl isocyanurate, trimaallyl isocyanurate, and bisarylnadiimide.

[0154] These compounds having ethylenically unsaturated groups can be used individually or in appropriate mixtures of two or more.

[0155] In the curable resin composition of the present invention, compounds having acid anhydride groups may be further incorporated. Any conventionally known compounds having acid anhydride groups can be used as the compounds that can be incorporated. Specific examples of compounds having acid anhydride groups include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic anhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride. Compounds having acid anhydride groups can be used alone or in combination of two or more. Furthermore, when the acid anhydride group reacts with the amine, an amical is formed. Further heating at 200°C to 300°C results in a dehydration reaction, forming an imide structure, which is a material with excellent heat resistance.

[0156] The curable resin composition of the present invention may further contain a curing accelerator (D). 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-diazabicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; triphenylphosphine, tributylphosphine, trio Examples include phosphines such as ctylphosphine, organometallic salts such as tin octoate, zinc octoate, 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, and salts such as sodium carbonate and lithium chloride.

[0157] Specific examples of hardening accelerators (D) are shown below. Examples of organic peroxide polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di- t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimeth Lu-2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3,-Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl Examples include peroxymalic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, t-butyl peroxyallyl monocarbonate, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0158] 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-carbonitride), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine)dihydrochloride, and 2,2'-azobis(2-methyl-N-phenylpropionamidine)dihydrochloride. 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine]dihydrochloride, 2,2 '-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidine-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,Examples include 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-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[0159] Furthermore, examples of curing accelerators (D) include phosphine compounds, compounds containing phosphonium salts, and imidazole compounds, and one or more of these can be used in combination. Imidazole compounds are particularly preferred. Imidazole compounds have excellent catalytic properties and can more reliably accelerate the polymerization reaction of maleimide resins (A) and (B).

[0160] Examples of imidazole compounds include, but are not limited to, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole. In particular, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferred. Using these compounds further accelerates the reaction of maleimide resins (A) and (B), resulting in the advantage of improved heat resistance of the resulting cured product. These can be used individually or in combination of two or more.

[0161] The phosphine compounds are not particularly limited, but examples include primary phosphines such as alkylphosphines like ethylphosphine and propylphosphine, and phenylphosphine; secondary phosphines such as dialkylphosphines like dimethylphosphine and diethylphosphine, diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; trialkylphosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, and trioctylphosphine; tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tripenzylphosphine, tritrillphosphine, tri-p-styrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, and tri-2-cyanoethylphosphine. Among these, tertiary phosphines are preferred. These can be used individually or in combination of two or more.

[0162] Compounds containing phosphonium salts include compounds containing tetraphenylphosphonium salts, alkyltriphenylphosphonium salts, and tetraalkylphosphonium. 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.

[0163] The curing accelerator (D) can be used alone or in combination of two or more types.

[0164] The content of the curing accelerator (D) is not particularly limited, but is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of reactive resin components.

[0165] The curable resin composition of the present invention may also contain, as component (E) other than the above-mentioned components, for example, a photopolymerization initiator, an inorganic filler, a mold release agent, a flame retardant, an ion trapping agent, an antioxidant, an adhesion promoter, a stress reduction agent, a colorant, or a coupling agent, to the extent that it does not impair the effects of the present invention.

[0166] The curable resin composition of the present invention may optionally contain a photopolymerization initiator. By curing not only by heat but also by ultraviolet irradiation, the crosslinking density can be further increased, improving heat resistance.

[0167] (Photopolymerization initiator) The photopolymerization initiator of the present invention is not particularly limited, and conventionally used ones can be used as appropriate, for example, acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyldimethyl ketal, thioxatone, 2-chlorothioxatone, 2-methylthioxatone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1 Examples of photopolymerization initiators include propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-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, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), and 2,4-dimethylthioxanthone. Such photopolymerization initiators may be used individually or in combination of two or more.

[0168] Among these, the photopolymerization initiator of the present invention is preferably one that efficiently generates radicals at exposure wavelengths of 310 to 436 nm (more preferably 365 nm), from the viewpoint of being able to form fine patterns using a reduction projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm) which is standardly used in the manufacturing process of semiconductor protective films, etc. Furthermore, maleimide groups generally do not undergo homopolymerization by radicals, and instead, a dimerization reaction of the bismaleimide compound proceeds mainly through reaction with radicals generated from the photopolymerization initiator, forming a crosslinked structure. For this reason, the inventors surmise that bismaleimide compounds are generally less reactive than acrylic compounds and the like which are commonly used as photopolymerizable compounds. Therefore, from the viewpoint of being able to generate radicals more efficiently and having high reactivity at exposure wavelengths of 310 to 436 nm (more preferably 365 nm), the photopolymerization initiator of the present invention is even more preferably a compound having an oxime structure or a thioxanthone structure.

[0169] Examples of such photopolymerization initiators include 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime) (BASF Japan, "IRGACURE OXE-01"), which has an oxime structure; ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (BASF Japan, "IRGACURE OXE-02"); and 2,4-dimethylthioxanthone (Nippon Kayaku Co., Ltd., "DETX-S"), which has a thioxanthone structure. While such photopolymerization initiators with high radical generation ability by light tend to be too reactive and difficult to control when used in the photopolymerization of ordinary acrylic compounds, they can be suitably used in the present invention.

[0170] (filling material) The curable resin composition of the present invention may further contain fillers to improve various properties such as film-forming properties and heat resistance. Preferably, the filler has insulating properties and does not inhibit transmission to a wavelength of 405 nm (h-ray). The fillers are not particularly limited, but examples include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass (e.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. These fillers can be used individually or in appropriate mixtures of two or more types.

[0171] Among these, it is preferable that one or more are selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers may be surface-treated with silane coupling agents or the like, as described later.

[0172] From the viewpoint of improving the heat resistance of the cured product obtained by curing the curable resin composition of the present invention and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include SFP-130MC from Denka Co., Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA from Admatex Co., Ltd.

[0173] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, and preferably 0.01 to 50 μm.

[0174] In the curable resin composition of the present invention, the content of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferable to have 1,000 parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less, per 100 parts by mass of resin solids in the curable resin composition. When a filler is included, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is usually 1 part by mass per 100 parts by mass of resin solids in the curable resin composition.

[0175] (Silane coupling agent and wetting / dispersing agent) The curable resin composition of the present invention may also be used in combination with a silane coupling agent and / or a wetting dispersant to improve the dispersibility of the filler and the adhesive strength between the polymer and / or resin and the filler. These silane coupling agents are not particularly limited as long as they are silane coupling agents commonly used for surface treatment of inorganic materials. Specific examples include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxylane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl- Aminosilanes such as 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N-dimethylamino)-propyl]trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl Epoxysilanes such as ethyltrimethoxysilane and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinylsilanes such as vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, and trimethoxy(4-vinylphenyl)silane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Methacrylsilanes such as toxysilane, 3-methacryloxypropyldimethoxymethylsilane, and 3-methacryloxypropyldiethoxymethylsilane; acrylicsilanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanatesilanes such as 3-isocyanatetopropyltrimethoxysilane and 3-isocyanatetopropyltriethoxysilane; isocyanuratesilanes such as tris-(trimethoxysilylpropyl)isocyanurate;Examples include mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride; acid anhydrides such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; and arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used individually or in appropriate mixtures of two or more.

[0176] In the curable resin composition of the present invention, the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass per 100 parts by mass of resin solids in the curable resin composition. The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include wetting and dispersing agents such as DISPERBYK®-110, 111, 118, 180, 161, BYK®-W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. These wetting and dispersing agents can be used individually or in appropriate mixtures of two or more. In the curable resin composition of the present invention, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass per 100 parts by mass of resin solids in the curable resin composition.

[0177] (Organic solvents) The curable resin composition of the present invention may optionally contain an organic solvent. Using an organic solvent allows for adjustment of the viscosity during the preparation of the curable resin composition. The type of organic solvent is not particularly limited, as long as it is capable of dissolving part or all of the resin in the curable resin composition. Specific examples, though not limited to them, include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosolve solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monobutyl ether; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, and γ-butyrolactone; polar solvents such as amides such as dimethylacetamide and dimethylformamide; nonpolar solvents such as toluene and aromatic hydrocarbons such as xylene and anisole; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; and sulfones such as tetramethylene sulfone. These organic solvents can be used individually or in appropriate mixtures of two or more.

[0178] (Other ingredients) The curable resin composition of the present invention may also contain various polymer compounds such as thermosetting resins, thermoplastic resins, and their oligomers and elastomers, which have not been previously mentioned; flame retardant compounds, which have not been previously mentioned; and additives, as long as the properties of the present invention are not impaired. These are not particularly limited as long as they are commonly used. For example, flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, etc. Additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments such as phthalocyanine blue and phthalocyanine green, carbon black, thickeners, lubricants, defoamers, surface modifiers, gloss agents, polymerization inhibitors, and curing accelerators. These components can be used individually or in appropriate mixtures of two or more. In the curable resin composition of the present invention, the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass of each component per 100 parts by mass of resin solids in the curable resin composition.

[0179] (Method for producing curable resin compositions) The curable resin composition of the present invention is prepared by appropriately mixing components (A) to (D) with, if necessary, a resin or compound, a photocuring initiator, a filler, other components, and additives. The resin composition of the present invention can be suitably used as a varnish when producing the resin sheet of the present invention, which will be described later.

[0180] The method for producing the curable resin composition of the present invention is not particularly limited, and for example, one method is to sequentially blend each of the above-mentioned components into a solvent and stir thoroughly.

[0181] During the production of the curable resin composition, known treatments (stirring, mixing, kneading, etc.) can be performed as needed to uniformly dissolve or disperse each component. Specifically, the dispersibility of the filler in the curable resin composition can be improved by performing a stirring and dispersion treatment using a stirring tank equipped with a stirrer having appropriate stirring capacity. The aforementioned stirring, mixing, and kneading treatments can be appropriately performed using known devices such as a stirring device for dispersion purposes such as an ultrasonic homogenizer, a mixing device for mixing purposes such as a three-roll mill, ball mill, bead mill, or sand mill, or a revolving or rotating type mixing device. Furthermore, when preparing the curable resin composition of the present invention, an organic solvent can be used as needed. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the curable resin composition, and specific examples are as described above.

[0182] The curable resin composition of the present invention may be prepolymerized. For example, a maleimide resin and a cyanate ester compound may be prepolymerized by heating them in the presence or absence of a catalyst, in the presence or absence of a solvent. Similarly, the maleimide resin of the present invention may be prepolymerized by adding, as necessary, an epoxy resin, an amine compound, a maleimide-based compound, a cyanate ester compound, a phenolic resin, an acid anhydride compound, and other additives.

[0183] (Application) The curable resin composition of the present invention can be used in applications requiring an insulating resin composition, and is not particularly limited, but can be used in applications such as photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and fiber-reinforced composite materials. Among these, the curable resin composition of the present invention is particularly suitable for use as an insulating layer in multilayer printed wiring boards or as a solder resist because it exhibits superior adhesion to chips and substrates, as well as excellent heat resistance and thermal stability.

[0184] (cured product) The cured product of the present invention is obtained by curing the curable resin composition of the present invention. The cured product is not particularly limited, but for example, it can be obtained by melting or dissolving the curable resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using heat or light. In the case of thermal curing, the curing temperature is not particularly limited, but from the viewpoint of efficient curing and preventing deterioration of the resulting cured product, it is preferably in the range of 120°C to 300°C. In the case of photocuring, the wavelength range of light is not particularly limited, but it is preferable to cure in the range of 100 nm to 500 nm, which allows for efficient curing with a photopolymerization initiator or the like.

[0185] (Resin sheet) The resin sheet of the present invention comprises a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the curable resin composition of the present invention. The resin sheet can be manufactured by coating the curable resin composition onto the support and drying it. The resin layer in the resin sheet of the present invention has excellent adhesion to chips and substrates, as well as excellent heat resistance and thermal stability.

[0186] The support can be any known material and is not particularly limited, but examples 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, triacetyl acetate film, and ethylene tetrafluoroethylene copolymer film; conductive foils such as copper foil and aluminum foil; glass plates, SUS plates, and FRP.

[0187] For resin films, those coated with a release agent on the surface are preferable to facilitate peeling from the resin layer. The thickness of the resin film is preferably in the range of 5 to 100 μm, and more preferably in the range of 10 to 50 μm. If the thickness is less than 5 μm, the support tends to tear easily when peeling, and if the thickness exceeds 100 μm, the resolution when exposing from the support tends to decrease.

[0188] Furthermore, the resin sheet of the present invention may have its resin layer protected by a protective film. By protecting the resin layer with a protective film, it is possible to prevent the adhesion of dust and other debris to the surface of the resin layer and prevent scratches. As the protective film, a film made of the same material as the resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 50 μm, and more preferably in the range of 5 to 40 μm. If the thickness is less than 1 μm, the handling of the protective film tends to decrease, and if it exceeds 50 μm, it tends to be less cost-effective. It is preferable that the adhesive force between the resin layer and the protective film is less than the adhesive force between the resin layer and the support.

[0189] The method for producing the resin sheet of the present invention is not particularly limited, but examples include a method in which the curable resin composition of the present invention is applied to a support and dried to remove the organic solvent in order to produce the resin sheet. The coating method can be carried out by known methods such as using a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, and squeeze coater. The drying can be carried out by heating in a dryer at 60 to 200°C for 1 to 60 minutes, for example.

[0190] From the viewpoint of preventing the diffusion of organic solvent in subsequent processes, the amount of organic solvent remaining in the resin layer is preferably 5% by mass or less of the total mass of the resin layer. From the viewpoint of improving handling, the thickness of the resin layer is preferably 1 to 50 μm.

[0191] The resin sheet of the present invention can be used for manufacturing the insulating layer of a multilayer printed circuit board.

[0192] (Prepreg) In the present invention, the prepreg comprises a substrate and a curable resin composition impregnated or coated onto the substrate. The method for producing the prepreg is not particularly limited, as long as it is a method of producing the prepreg by combining the curable resin composition of the present invention with a substrate. For example, the prepreg of the present invention can be produced by impregnating or coating the substrate with the curable resin composition of the present invention and then partially curing (B-stage) it by drying it in a dryer at 120 to 220°C for about 2 to 15 minutes. In this case, the amount of curable resin composition adhering to the substrate, that is, the content of the curable resin composition (including filler) per 100 parts by mass of the partially cured prepreg, is preferably in the range of 20 to 99 parts by mass.

[0193] When manufacturing prepregs, known substrates used in various printed circuit board materials can be used. The substrate is not particularly limited, but examples include glass fibers, inorganic fibers other than glass such as quartz; organic fibers such as polyimide, polyamide, and polyester; and woven fabrics such as liquid crystal polyester. The substrate can take the form of woven fabric, nonwoven fabric, roving, chopped strand mat, or surfacing mat, and any of these may be used. The substrate can be used individually or in combination of two or more types. Among woven fabrics, those that have undergone ultra-opening or densification treatment are particularly preferred from the viewpoint of dimensional stability. Liquid crystal polyester woven fabric is preferred from the viewpoint of electrical properties. The thickness of the substrate is not particularly limited, but for laminate applications, a range of 0.01 to 0.2 mm is preferred.

[0194] (Metal foil-clad laminate) In the present invention, a metal foil-clad laminate comprises a layer containing at least one selected from the group consisting of the resin sheet and prepreg of the present invention, and a metal foil disposed on one or both sides of the layer, wherein the layer contains a cured product of the curable resin composition of the present invention. When using a prepreg, for example, it can be manufactured by laminating a single prepreg or a stack of prepregs with a metal foil such as copper or aluminum placed on one or both sides. The metal foil used here is not particularly limited as long as it is used in printed circuit board materials, but copper foil such as rolled copper foil and electrolytic copper foil is preferred. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, and more preferably 3 to 35 μm. As for the molding conditions, the methods used when manufacturing laminates and multilayer boards for printed circuit boards can be employed. For example, using a multi-stage press, multi-stage vacuum press, continuous molding machine, or autoclave molding machine, with a temperature of 180-350°C, a heating time of 100-300 minutes, and a surface pressure of 20-100 kg / cm². 2 The metal foil-clad laminate of the present invention can be manufactured by lamination molding under the conditions described above. Furthermore, a multilayer board can be manufactured by laminating the aforementioned prepreg with a separately manufactured wiring board for the inner layer. As an example of the manufacturing method for the multilayer board, 35 μm copper foil is placed on both sides of one sheet of the aforementioned prepreg, and after lamination molding under the conditions described above, an inner layer circuit is formed, and this circuit is subjected to a blackening treatment to form an inner layer circuit board. Furthermore, this inner layer circuit board and the aforementioned prepreg are arranged alternately one sheet at a time, and copper foil is placed as the outermost layer, and lamination molding is performed under the conditions described above, preferably under vacuum. In this way, a multilayer board can be manufactured.

[0195] Metal foil-clad laminates can be suitably used as printed circuit boards by further pattern formation. Printed circuit boards can be manufactured according to conventional methods, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed circuit board is shown below. First, the aforementioned metal foil-clad laminate is prepared. Next, an inner layer substrate is fabricated by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase adhesive strength as needed, and then the required number of prepregs are stacked on the inner layer circuit surface. Furthermore, metal foil for the outer layer circuit is laminated on the outside, and the two layers are integrally molded by heating and pressurizing. In this way, a multilayer laminate is manufactured in which an insulating layer consisting of a substrate and a cured product of a curable resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, holes for through-holes and via holes are drilled in this multilayer laminate, and then a plated metal film is formed on the walls of these holes to allow conductivity between the inner layer circuit and the metal foil for the outer layer circuit. Furthermore, the outer layer circuit is formed by etching the metal foil for the outer layer circuit, thereby manufacturing a printed circuit board.

[0196] The printed circuit board obtained in the above manufacturing example has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, wherein the insulating layer contains the curable resin composition of the present invention. For example, the prepreg of the present invention (a base material and the curable resin composition of the present invention impregnated or coated therein), and the layer of the curable resin composition of the metal foil-clad laminate of the present invention (a layer made of the curable resin composition of the present invention) can constitute an insulating layer containing the curable resin composition of the present invention.

[0197] (Multilayer printed circuit board) In the present invention, a multilayer printed circuit board has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, wherein the insulating layer contains the curable resin composition of the present invention. The insulating layer can also be obtained, for example, by stacking and curing one or more resin sheets. Instead of the resin sheets of the present invention, a prepreg of the present invention may be used. The multilayer printed circuit board of the present invention can be manufactured according to conventional methods, and the manufacturing method is not particularly limited. An example of a method for manufacturing a multilayer printed circuit board is shown below. First, the aforementioned metal foil-clad laminate is prepared. Next, an inner layer substrate is fabricated by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase adhesive strength as needed, and then the required number of prepregs are stacked on the surface of the inner layer circuit. Furthermore, metal foil for the outer layer circuit is laminated on the outside and integrally molded by heating and pressurizing. In this way, a multilayer laminate is manufactured in which an insulating layer made of a substrate and a cured product of a curable resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, holes for through holes and via holes are drilled in this multilayer laminate, and then a plated metal film is formed on the walls of these holes to allow conductivity between the inner layer circuit and the metal foil for the outer layer circuit. Furthermore, the outer layer circuit is formed by etching the metal foil for the outer layer circuit, thereby manufacturing a multilayer printed circuit board.

[0198] The printed circuit board obtained in the above manufacturing example has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, wherein the insulating layer contains the curable resin composition of the present invention. For example, the prepreg of the present invention (a base material and the curable resin composition of the present invention impregnated or coated therein), and the layer of the curable resin composition of the metal foil-clad laminate of the present invention (a layer made of the curable resin composition of the present invention) can constitute an insulating layer containing the curable resin composition of the present invention.

[0199] (Sealing material) In the present invention, the sealing material includes the curable resin composition of the present invention. The method for producing the sealing material is not particularly limited and can be any method that is generally known. For example, the sealing material can be produced by mixing the curable resin composition of the present invention with various known additives or solvents commonly used in sealing material applications using a known mixer. The method for adding the maleimide compound, various additives, and solvents of the present invention during mixing is not particularly limited and can be any method that is generally known.

[0200] (Fiber-reinforced composite material) In the present invention, the fiber-reinforced composite material comprises the curable resin composition of the present invention and reinforcing fibers. Generally known reinforcing fibers can be used and are not particularly limited. Examples include 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; aramid fibers; boron fibers; PBO fibers; high-strength polyethylene fibers; alumina fibers; and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited and can be appropriately selected from woven fabrics, nonwoven fabrics, mats, knits, braids, unidirectional strands, rovings, and chopped materials. Furthermore, preforms (laminated woven fabrics made of reinforcing fibers, or those sewn together with stitching threads, or fiber structures such as three-dimensional woven fabrics or braided fabrics) can also be applied as the form of the reinforcing fibers.

[0201] The manufacturing method for these fiber-reinforced composite materials is not particularly limited and can be any method that is generally known. Examples include the liquid composite molding method, the resin film infusion method, the filament winding method, the hand layup method, and the pultrusion method. Among these, the resin transfer molding method, which is a type of liquid composite molding method, is preferable for mass production of relatively complex composite materials in a short time because it can accommodate various applications, as materials other than preforms, such as metal plates, foam cores, and honeycomb cores, can be pre-set in the mold.

[0202] (glue) In the present invention, the adhesive comprises the curable resin composition of the present invention. The method for producing the adhesive is not particularly limited and can be any method that is generally known. For example, the adhesive can be produced by mixing the curable resin composition of the present invention with various known additives or solvents commonly used in adhesive applications using a known mixer. The method for adding the maleimide compound, various additives, and solvents of the present invention during mixing is not particularly limited and can be any method that is generally known.

[0203] (Semiconductor device) In the present invention, the semiconductor device has the curable resin composition of the present invention. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting semiconductor chips on conductive locations of the multilayer printed circuit board of the present invention. Here, conductive locations are locations on the multilayer printed circuit board that transmit electrical signals, and these locations may be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0204] The method of mounting semiconductor chips when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting methods, flip-chip mounting methods, bumpless build-up layer (BBUL) mounting methods, anisotropic conductive film (ACF) mounting methods, and non-conductive film (NCF) mounting methods.

[0205] Furthermore, semiconductor devices can also be manufactured by forming an insulating layer containing the curable resin composition of the present invention on a semiconductor chip or a substrate on which a semiconductor chip is mounted. The substrate on which the semiconductor chip is mounted may be in the shape of a wafer or a panel. After formation, it can be manufactured using the same method as for the multilayer printed circuit board described above. [Examples]

[0206] The present invention will be described more specifically below based on examples and comparative examples, but the present invention is not limited to the following examples. Synthesis Examples 3 and 4 refer to Patent Document 4, and Synthesis Examples 5 and 6 refer to Patent Document 6. In this text, "parts" and "%" refer to "parts by weight" and "weight %", respectively. The GPC (gel permeation chromatography) measurement conditions for synthesis examples 1 and 2 are as follows. ·Model: GPC TOSOH HLC-8220GPC • Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C ·Detector: RI (Differential Refractometer) ·Molecular Weight Standard: Polystyrene

[0207] <Synthesis of Maleimide Resin (A)>[[]] [Synthesis Example 1 (A-1)] 110 g of toluene and 36 g of N-methylpyrrolidone were charged into a 500 ml round-bottom flask equipped with a Teflon (registered trademark)-coated stirring bar. Next, 85.6 g (0.16 mol) of PRIAMINE 1074 (manufactured by Clariant Japan K.K.) was added, and then 15.4 g (0.16 mol) of methanesulfonic anhydride was slowly added to form a salt. The mixture was stirred for approximately 10 minutes, and then 1,2,4,5-cyclohexanetetracarboxylic dianhydride (24.5 g, 0.08 mol) was slowly added to the stirred mixture. A Dean-Stark trap and a condenser were attached to the flask. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water generated from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 18.8 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water generated. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3) to remove salts and unreacted raw materials. Then, the solvent was removed under vacuum to obtain 108 g (yield 90%, Mw = 3,600) of an amber wax-like maleimide resin (A-1).

[0208] [Synthesis Example 2 (A-2)] 100 g of toluene and 33 g of N-methylpyrrolidone were charged into a 500 ml round-bottomed flask equipped with a Teflon (registered trademark)-coated stirring bar. Next, 80.2 g (0.16 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) was added, and then 14.4 g (0.16 mol) of anhydrous methanesulfonic acid was slowly added to form a salt. The mixture was stirred for approximately 10 minutes to mix, and then 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (22.5 g, 0.08 mol) was slowly added to the stirred mixture. A Dean-Stark trap and a condenser were attached to the flask. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water generated from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 17.6 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water generated. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3 times) to remove salts and unreacted raw materials. Thereafter, the solvent was removed under vacuum to obtain 104 g (yield 93%, Mw = 3,700) of a dark amber liquid maleimide resin (A-2).

[0209] The various measurement conditions for Synthesis Examples 3 to 6 are as follows. · Softening point: Measured by a method according to JIS K-7234 · Acid value: Measured by a method according to JIS K-0700:1992 · GPC (gel permeation chromatography) analysis Column: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 0.5 ml / min. Column temperature: 40 °C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) · HPLC (high performance liquid chromatography) analysis Column: Inertsil ODS-2 Flow rate: 1.0ml / min. Column temperature: 40℃ Solvents used: Acetonitrile, Water Detector: Photodiode array (200nm)

[0210] [Synthesis Example 3] In a flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer, 279 parts aniline, 100 parts toluene, 146 parts m-di(α-hydroxyisopropyl)benzene, and 50 parts activated clay were charged. The mixture was heated to 170°C over 6 hours while removing water and toluene by distillation, and the reaction was carried out at this temperature for 13 hours. After cooling to room temperature, 230 parts toluene was added, and the activated clay was removed by filtration. Next, 241 parts of the aromatic amine resin (A1) described in (9) were obtained by distilling off excess aniline and toluene from the oil layer under reduced pressure using a rotary evaporator. The amine equivalent of the aromatic amine resin (A1) was 179 g / eq, and the softening point was 46.5°C. GPC analysis (RI) revealed that the n=1 compound was 73%, and HPLC analysis showed that 1,3-bis(p-aminocumyl)benzene in the n=1 compound was 49%. Therefore, the total amount of 1,3-bis(p-aminocumyl)benzene in the aromatic amine resin was 36%.

[0211] [Synthesis example 4 (B-1)] A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 147 parts maleic anhydride, 300 parts toluene, and 4 parts methanesulfonic acid, and heated under reflux. Next, a resin solution prepared by dissolving 197 parts aromatic amine resin (a1) in 95 parts N-methyl-2-pyrrolidone and 100 parts toluene was added dropwise over 3 hours while maintaining reflux. During this time, the condensed water and toluene that formed azeotropically under reflux conditions were cooled and separated in the Dean-Stark azeotropic distillation trap. The toluene, which was the organic layer, was returned to the system, and the water was discharged from the system. After the addition of the resin solution was complete, the reaction was carried out for 6 hours while maintaining reflux and performing dehydration. After the reaction was complete, the mixture was washed with water four times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure and heating below 70°C. Next, 2 parts of methanesulfonic acid were added, and the reaction was carried out under reflux for 2 hours. After the reaction was complete, the mixture was washed with water four times until the washing water became neutral, and then water was removed from the system by azeotropic distillation of toluene and water under reduced pressure and heating below 70°C. Finally, the toluene was completely distilled off under reduced pressure and heating to obtain the maleimide resin (B-1) represented by formula (10). The softening point of the obtained maleimide resin (B-1) was 100°C, and the acid value was 9 mgKOH / g.

[0212] [Synthesis Example 5] In a flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer, 290 parts of 2-ethylaniline, 120 parts of toluene, 117 parts of m-di(α-hydroxyisopropyl)benzene, and 24 parts of activated clay were charged. The reaction was carried out at 140°C for 8 hours and then at 170°C for 16 hours, while removing water and toluene by distillation. After cooling to room temperature, 320 parts of toluene were added, and the activated clay was removed by filtration. Next, 222 parts of the aromatic amine resin (a2) represented in (9) were obtained by distilling off excess 2-ethylaniline and toluene from the oil layer under heated reduced pressure using a rotary evaporator. The amine equivalent of the aromatic amine resin was 201 g / eq, and the temperature was at room temperature. GPC analysis (RI) showed that n=1 was 89%.

[0213] [Synthesis example 6 (B-2)] A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 147 parts maleic anhydride, 300 parts toluene, and 4 parts methanesulfonic acid, and heated under reflux. Next, a resin solution prepared by dissolving 201 parts of aromatic amine resin (a2) prepared in Synthesis Example 5 in 140 parts toluene was added dropwise over 7 hours while maintaining reflux. During this time, the condensed water and toluene that formed azeotropically under reflux conditions were cooled and separated in the Dean-Stark azeotropic distillation trap. The toluene, which is the organic layer, was returned to the system, and the water was discharged from the system. After the addition of the resin solution was complete, the reaction was carried out for 6 hours while maintaining reflux and performing dehydration. After the reaction was complete, the mixture was washed with water four times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure and heating below 70°C. Next, 2 parts of methanesulfonic acid were added, and the reaction was carried out under reflux for 4 hours. After the reaction was complete, the mixture was washed with water three times until the washing water became neutral, and then water was removed from the system by azeotropic distillation of toluene and water under reduced pressure and heating below 70°C. Finally, the toluene was completely removed by distillation under reduced pressure and heating to obtain the maleimide resin (B-2) represented by formula (10). The softening point of the obtained maleimide resin (B-2) was 93°C, and the acid value was 9 mgKOH / g. GPC analysis (RI) showed that n=1 was 87%.

[0214] [Synthesis example 7 (C-2)] In a flask equipped with a thermometer, condenser, and stirrer, 225 g of XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 74.8°C, epoxy equivalent 255 g / eq.), 72.1 g of acrylic acid, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added to a total solid content of 80%. The mixture was reacted at 100°C for 24 hours to obtain an epoxy carboxylate compound solution, which was a reaction intermediate. Next, 140 g of 1,2,3,6-tetrahydrophthalic anhydride (THPA) (trade name: Ricacid TH, manufactured by Shin Nippon Rika Co., Ltd.) was added to the obtained reactive epoxy carboxylate compound solution as a polybasic acid anhydride, and propylene glycol monomethyl ether monoacetate was added as a solvent to achieve a solid content of 65%. The mixture was reacted at 100°C for 6 hours to obtain reactive polycarboxylic acid compound (C-2). The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid compound (C-2) was 110.

[0215] [Examples 1-5] <Preparation of curable resin compositions and resin films> The curable resin compositions of Examples 1 to 5 were prepared by blending the respective components shown below in the composition shown in Table 1. Using an applicator, the curable resin composition was applied onto a 12-μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil & Powder Co., Ltd.) on a hot plate heated to 60°C, and heat treatment was performed at 120°C for 30 minutes using an oven to produce a resin film in a B-stage state with a thickness of 100 μm. Thereafter, another 12-μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil & Powder Co., Ltd.) was laminated onto the obtained resin film in the B-stage state using a laminator, and heating was performed at 220°C for 2 hours to complete thermosetting. Regarding Example 4, the resin film in the B-stage state was exposed to an ultra-high pressure mercury lamp (USH-500BY1 manufactured by Ushio Denki Co., Ltd.) at 100 mJ / cm 2 (irradiation intensity 10 mW / cm 2 , for 10 seconds), and then a 12-μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil & Powder Co., Ltd.) was laminated onto it using a laminator, and heating was performed at 220°C for 2 hours to complete thermosetting.

[0216] <(A) Maleimide resin> (A-1) The maleimide resin represented by formula (2) The maleimide resin (A-1) of Synthesis Example 1 (compound represented by the following formula (20), high-viscosity liquid at 25°C)

[0217]

Chemical formula

[0218] (A-2) The maleimide resin represented by formula (2) The maleimide resin (A-2) of Synthesis Example 2 (compound represented by the following formula (21), high-viscosity liquid at 25°C)

[0219]

Chemical formula

[0220] (B) Maleimide resin (B-1) Maleimide resin represented by formula (10). (R in formula (10) represents a hydrogen atom) Maleimide resin (B-1) in synthesis example 4 (B-2) Maleimide resin represented by formula (10). (In formula (10), R is an ethyl group.) Maleimide resin (B-2) in synthesis example 6

[0221] <(C) Thermosetting resin> (C-1) BMI-689 (a compound represented by formula (22) below, manufactured by DESIGNER MOLECURES Inc., liquid at 25°C)

[0222] [ka]

[0223] (C-2) Compound represented by the following formula (23) Compound (C-2) from Synthesis Example 7

[0224] [ka]

[0225] <(D) Curing accelerator> (D-1) Perkmyl D (Dicumyl Peroxide (manufactured by Nippon Oil & Fats Co., Ltd.)) (D-2) 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

[0226] <(E) Photopolymerization initiator> (E-1) Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (BASF Japan, "IRGACURE OXE-02")

[0227] <Fabrication of copper foil laminates> A resin film peeled off by etching and two copper foils (CF-T4X-SV (product name), manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) were laminated so that the mirror surface of the copper foils faced the resin film. The laminates were then heat-pressed together at 220°C, 1.0 MPa, and for 2 hours using a hot press to obtain a copper foil laminate in which the copper foil, cured resin film, and copper foil were laminated in that order.

[0228] <Characteristic Evaluation> The following properties were measured for the prepared curable resin composition and copper foil laminate. The results are shown in Table 1.

[0229] [compatibility] Visual compatibility refers to the state of the curable resin composition after mixing components (A) to (D) and stirring, as observed visually. Good compatibility means that there are no precipitates, etc., and that it is possible to apply it to a substrate, etc. Poor compatibility means that there are precipitates, etc., and that it is difficult to apply it to a substrate, etc. (Evaluation Criteria) ○: No precipitates ×: Precipitation present

[0230] [Haze value] In accordance with JIS K7136, the haze was calculated using the following formula (1) by irradiating the curable resin composition with light using a color and turbidity simultaneous measuring instrument (Nippon Denshoku, COH400) at 25°C, and comparing the total light transmittance (Tt), which represents the total amount of light transmitted, with the diffuse light transmittance (Td), which represents the amount of light diffused by the sheet. The total light transmittance (Tt) is the sum of the parallel light transmittance (Tp), which is transmitted coaxially with the incident light, and the diffuse light transmittance (Td). Hayes (H) = Td / Tt × 100 ... (1) The haze of the resulting curable resin composition was evaluated in four stages. ◎: Haze is less than 30 ○: Haze is 30 or higher, and less than 50. △: Haze is 50 or higher, and less than 70. ×: Haze is 70 or higher

[0231] [Dielectric properties] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut to prepare a 10cm x 5cm test specimen. The relative permittivity and dielectric loss tangent of the obtained test specimen were measured at 10GHz using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.). After measurement, the test specimen was immersed in water for 24 hours to absorb water, then removed from the water, wiped dry, and left in an environment of 25°C and 20% humidity for one day, after which the relative permittivity and dielectric loss tangent were measured again at 10GHz.

[0232] [Tensile modulus of elasticity] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut to prepare 6cm x 5mm test specimens. The tensile modulus and elongation of the obtained test specimens were measured using a tensile testing machine (product name "RTG-1201", manufactured by A&D Co., Ltd.) at a speed of 5mm / min at 25°C.

[0233] [Heat resistance] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut into 4 mm squares, and 1.0 to 5.0 mg was weighed into a measuring pan. The 5% weight loss rate (Td5) was measured under conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. The measuring device used was a TGA / DSC1 (METTLER TOLEDO). [Glass transition temperature] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut to prepare 5cm x 5mm test specimens. The obtained test specimens were measured using a dynamic viscoelasticity tester (DMA: product name "RSA-G2", manufactured by TA Instruments), and the temperature at which tanδ reached its maximum value was determined as the glass transition temperature. Furthermore, the tanδ peak waveform was examined from the perspective of compatibility, and the number of peaks was counted.

[0234] [Water absorption rate] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut to prepare 10cm x 5cm test specimens. The obtained test specimens were immersed in water for 24 hours to allow water absorption, then removed from the water and wiped dry. The weight increase rate of the test specimens was defined as the water absorption rate.

[0235] [HAST resistance] A curable resin composition was applied to an Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd.: base imide thickness 25 μm, Cu thickness 18 μm) with a comb-shaped pattern of L / S = 100 μm / 100 μm formed by screen printing to a thickness of 25 μm. The coating was dried in a hot air dryer at 120°C for 60 minutes. Next, Aflex (Grade: 25N NT) (manufactured by AGC Inc.) was placed over the resin surface and heated at 220°C for 2 hours to obtain a test substrate for HAST evaluation. The electrode portions of the obtained substrate were wired together with solder, placed in an environment of 130°C and 85% RH, and a voltage of 100V was applied to obtain a resistance value of 1 × 10⁻¹⁶. 8 The time it took for the value to drop below Ω was measured. For Example 4, after solvent drying, the material was exposed to a high-pressure mercury lamp (USH-500BY1, manufactured by Ushio Inc.) at a rate of 100 mJ / cm2 (irradiation intensity 10 mW / cm2, for 10 seconds). Then, Aflex (Grade: 25N NT) (manufactured by AGC Inc.) was bonded to the material using a laminator, and the material was heated at 220°C for 2 hours to complete the thermal curing process. ○...100 hours or more △...More than 20 hours but less than 100 hours ×‥20 hours or less

[0236] [Table 1]

[0237] As is clear from the results shown in Table 1, the curable resin compositions of Examples 1 to 5 exhibited good adhesion to the substrate, and the cured products were confirmed to have low dielectric properties, low elastic modulus, high heat resistance, and low water absorption. Therefore, the curable resin compositions of the present invention can be used in applications such as photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminate applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and fiber-reinforced composite materials. This makes it possible to dramatically improve the properties of laminates such as printed circuit boards and electronic components such as semiconductor devices.

[0238] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications are possible without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Patent Application No. 2021-056835) filed on March 30, 2021, which is incorporated by reference in its entirety. All references cited herein are incorporated as a whole.

Claims

1. A maleimide resin (A) having a cyclic imide bond is obtained by reacting a diamine (a-1) derived from a dimer acid with a tetracarboxylic dianhydride (a-2) and maleic anhydride. Maleimide resin (B) represented by the following formula (1), Hardening accelerator (D), A curable resin composition comprising, wherein components (A), (B), and (D) are compatible, A curable resin composition in which, in the total amount of the curable resin composition, the content of component (A) is 30% by weight or more and less than 95% by weight, and the content of component (B) is 3% by weight or more and less than 50% by weight, wherein the content of component (A) is greater than that of component (B). 【Chemistry 1】 (In formula (1), each of the multiple R's independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value is 1 < n < 5.)

2. The curable resin composition according to claim 1, wherein the component (A) is represented by the following formula (2). 【Chemistry 2】 (In formula (2), R １ represents a divalent hydrocarbon group (a) derived from dimer acid, and R ２ represents a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid, and R ３ represents any one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid, and R ４ and R ５ each independently represent one or more organic groups selected from a tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure and having 6 to 40 carbon atoms, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure connected to each other, and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. R ４ and R ５ contain 5 to 95 mol% when the total amount is 100 mol%. m is an integer from 1 to 30, n is an integer from 0 to 30, and when m is 2 or more, a plurality of R １ and R ４ may be the same or different from each other, and when n is 2 or more, a plurality of R ２ and R ５ may be the same or different from each other. )

3. The curable resin composition according to claim 1 or 2, wherein the component (a-2) is represented by the following formula (3-a). 【Transformation 3】 (In formula (3-a), R ６ This refers to a tetravalent organic group having 4 to 40 carbon atoms and containing a hydrocarbon ring; this organic group may also contain an aromatic ring.

4. The curable resin composition according to claim 3, wherein the component (a-2) is selected from the group consisting of the following formulas (4-1a) to (4-11a). 【Chemistry 4】 (In formula (4-4a), X １ X is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms. In formula (4-6a), X ２ (These are direct bonds, oxygen atoms, sulfur atoms, sulfonyl groups, divalent organic groups with 1 to 3 carbon atoms, or arylene groups.)

5. A curable resin composition according to any one of claims 1 to 4, further comprising a thermosetting resin (C) other than component (A) and component (B), wherein components (A) to (D) are miscible.

6. The curable resin composition according to claim 5, wherein component (C) is one or more selected from the group consisting of maleimide compounds other than components (A) and (B), cyanate ester compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

7. The curable resin composition according to claim 5 or 6, wherein the component (C) is a compound represented by the following formula (5). 【Transformation 5】 (In formula (5), R ａ , R ｂ Each of these is independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 1 to 16 carbon atoms. Na represents a number from 1 to 16, and nb represents a number from 1 to 16. na and nb may be the same or different.

8. The curable resin composition according to any one of claims 1 to 7, wherein the component (a-2) is a compound represented by the following formula (6). 【Transformation 6】

9. The curable resin composition according to any one of claims 1 to 7, wherein the component (a-2) is a compound represented by the following formula (7). 【Transformation 7】

10. The curable resin composition according to any one of claims 1 to 9, wherein component (D) comprises at least one selected from a thermal radical polymerization initiator and an imidazole compound.

11. The curable resin composition according to claim 10, wherein the thermal radical polymerization initiator is an organic peroxide.

12. A curable resin composition according to any one of claims 1 to 11, wherein the haze value at an optical path length of 10 mm, as measured in accordance with JIS K7136, is less than 50.

13. A resin sheet comprising the curable resin composition according to any one of claims 1 to 12.

14. A cured product obtained by curing a curable resin composition according to any one of claims 1 to 12.

15. A semiconductor element and a semiconductor substrate comprising the cured product according to claim 14 as at least one selected from the group consisting of a surface protective film, an interlayer insulating film, an insulating film for a redistribution layer, and an underfill.

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