JP7706849B2 - Curable resin composition, semiconductor encapsulant, adhesive, adhesive film, prepreg, interlayer insulating material, and printed wiring board - Google Patents

Description

The present invention relates to a curable resin composition, a semiconductor encapsulant, an adhesive, an adhesive film, a prepreg, an interlayer insulating material, and a printed wiring board.

In recent years, the next-generation communication system known as 5G (millimeter wave region of 26 GHz to 80 GHz) has become popular, and the development of the next-generation communication system known as 6G has also begun, aiming to realize faster, larger capacity, and lower latency communication than ever before. In order to realize these communication systems, materials for the high frequency band of 3 to 80 GHz are required, and reducing transmission loss as a noise countermeasure is essential.
Transmission loss is the sum of conductor loss and dielectric loss, and reducing conductor loss requires low surface roughness of the metal foil used. On the other hand, since dielectric loss is proportional to the product of the square root of the relative dielectric constant and the dielectric loss tangent, there is a demand for the development of insulating materials with excellent dielectric properties (low relative dielectric constant and low dielectric loss tangent).
Among these, insulating materials with excellent dielectric properties are required for circuit board applications. Reactive polyphenylene ether resin (PPE) is being used for rigid circuit boards, while liquid crystal polymer (LCP) and modified polyimide (MPI) with improved properties are being used for flexible printed circuit boards (FPC).

In response to this, it has been reported that maleimide compounds (special maleimide compounds) having substantially a dimer diamine skeleton (skeleton derived from dimer acid) are used as the main resin for substrates (Patent Documents 1 to 4). Contrary to the properties of general maleimide resins, special maleimide compounds have a low glass transition temperature (Tg) and a high coefficient of thermal expansion (CTE), but also have excellent dielectric properties, flexible properties, excellent adhesion to metals, and the possibility of (high) multi-layering because they are thermosetting resins, and have many other advantages, and have been researched and developed over a wide range. However, the use of special maleimide compounds alone has been the norm.
As described above, the dielectric loss is proportional to the product of the square root of the relative dielectric constant and the dielectric loss tangent, and therefore it is more important to reduce the dielectric loss tangent.

On the other hand, it has been reported that resin materials using a maleimide compound having a trimer triamine skeleton (a skeleton derived from trimer acid) as the main resin for substrates have excellent heat resistance, mechanical strength, dielectric properties, etc. (Patent Documents 5 and 6).
Generally, dimer acid and trimer acid are a mixture, and are generally called dimer acid in many cases. The same is true for dimer diamine and trimer triamine derived from dimer acid and trimer acid, and are generally called dimer diamine. It is well known that the ratio of dimer diamine and trimer triamine varies depending on the product even in the commercially available product of the compound called dimer diamine (Patent Document 7, Non-Patent Document 1).

JP 2016-131243 A JP 2016-131244 A International Publication No. 2016/114287 JP 2018-201024 A JP 2019-182932 A WO 2020/45408 JP 2017-186551 A

Journal of the Society of Organic Synthetic Chemistry, 1967, 25(2), 180-183

Against this background, we have synthesized and examined maleimide compounds having a structure derived from these trimer triamine skeletons, and have found that cured products of compositions containing maleimide compounds having a structure derived from a trimer triamine skeleton have high storage modulus and hardness, and are therefore prone to warping and cracking, have high relative dielectric constants and dielectric tangents at high frequencies, and are significantly affected by heating, resulting in poor heat resistance.
Therefore, the present invention aims to provide a curable resin composition which has low elasticity and low hardness and therefore little warping after curing, has excellent crack resistance, and exhibits excellent dielectric properties even at high frequencies, and which gives a cured product whose dielectric properties change little even after being left at high temperatures for a long period of time, and further aims to provide a semiconductor encapsulating material, an adhesive, an adhesive film, a prepreg, an interlayer insulating material, and a printed wiring board containing the same.

As a result of extensive research to solve the above problems, the inventors discovered that the following resin composition can achieve the above objective, and thus completed the present invention.

（式（１）中、Ａは独立してダイマー酸及びトリマー酸由来の炭化水素基を示し、Ｂは独立して環状構造を含む４価の有機基を示し、ｎは１～１０００である。）
及び
（Ｂ）触媒
を含有する硬化性樹脂組成物であって、
式（１）中のＡは、ダイマー酸及びトリマー酸由来の炭化水素基のうちダイマー酸由来の炭化水素基が占める割合が９５質量％以上であって、かつ水添処理された基である、硬化性樹脂組成物。
［２］
ＪＩＳ Ｋ７２４４－４：１９９９に記載の方法に準じ、２５℃の測定温度で、動的粘弾性測定装置を用いて、周波数１０Ｈｚ、温度範囲－５０℃～２００℃、昇温速度５℃／分で測定した、硬化性樹脂組成物の硬化物の貯蔵弾性率が、１０００ＭＰａ未満である［１］に記載の硬化性樹脂組成物。
［３］
ＪＩＳ Ｋ ６２５３－３：２０１２に記載の方法に準じ、２５℃の測定温度で、デュロメータタイプＤの硬度計を用いて測定した、硬化性樹脂組成物の硬化物の硬度が、Ｄ５０以下である［１］又は［２］に記載の硬化性樹脂組成物。
［４］
（Ｂ）成分の触媒が有機過酸化物、アニオン重合開始剤及び光硬化開始剤から選ばれる少なくとも１種である［１］～［３］のいずれかに記載の硬化性樹脂組成物。
［５］
［１］～［４］のいずれかに記載の硬化性樹脂組成物からなる半導体封止材。
［６］
［１］～［４］のいずれかに記載の硬化性樹脂組成物からなる接着剤。
［７］
［１］～［４］のいずれかに記載の硬化性樹脂組成物からなる接着フィルム。
［８］
［１］～［４］のいずれかに記載の硬化性樹脂組成物と繊維基材からなるプリプレグ。
［９］
［１］～［４］のいずれかに記載の硬化性樹脂組成物からなる層間絶縁材料。
［１０］
［１］～［４］のいずれかに記載の硬化性樹脂組成物の硬化物を有するプリント配線板。 That is, the present invention provides the following curable resin composition.
[1]
(A) A maleimide compound represented by the following general formula (1):

(In formula (1), A independently represents a hydrocarbon group derived from a dimer acid or a trimer acid, B independently represents a tetravalent organic group containing a cyclic structure, and n is 1 to 1,000.)
and (B) a catalyst,
A curable resin composition, wherein A in formula (1) is a group in which the proportion of hydrocarbon groups derived from a dimer acid and a trimer acid is 95 mass% or more, and which has been hydrogenated.
[2]
The curable resin composition according to [1], wherein the storage modulus of a cured product of the curable resin composition is less than 1000 MPa, as measured using a dynamic viscoelasticity measuring device at a measurement temperature of 25°C, a frequency of 10 Hz, a temperature range of -50°C to 200°C, and a heating rate of 5°C/min in accordance with the method described in JIS K7244-4:1999.
[3]
[1] or [2], wherein the hardness of a cured product of the curable resin composition is D50 or less, as measured using a durometer type D hardness tester at a measurement temperature of 25 ° C. in accordance with the method described in JIS K 6253-3:2012.
[4]
The curable resin composition according to any one of [1] to [3], wherein the catalyst of the component (B) is at least one selected from the group consisting of organic peroxides, anionic polymerization initiators, and photocuring initiators.
[5]
A semiconductor encapsulant comprising the curable resin composition according to any one of [1] to [4].
[6]
An adhesive comprising the curable resin composition according to any one of [1] to [4].
[7]
An adhesive film comprising the curable resin composition according to any one of [1] to [4].
[8]
A prepreg comprising the curable resin composition according to any one of [1] to [4] and a fiber base material.
[9]
An interlayer insulating material comprising the curable resin composition according to any one of [1] to [4].
[10]
A printed wiring board having a cured product of the curable resin composition according to any one of [1] to [4].

The curable resin composition of the present invention has low elasticity and low hardness, so warping after curing is small, and further has excellent crack resistance and excellent dielectric properties even at high frequencies, and gives a cured product whose dielectric properties change little even after being left at high temperatures for a long period of time. Therefore, the curable resin composition of the present invention is useful as a semiconductor encapsulant, adhesive, adhesive film, prepreg, interlayer insulating material, and printed wiring board.

FIG. 2 is a cross-sectional view showing an example of the prepreg of the present invention. FIG. 2 is a cross-sectional view showing an example of the laminate of the present invention. 1 is a cross-sectional view showing an example of a printed wiring board of the present invention.

The present invention will be explained in more detail below.

式（１）中、Ａは独立してダイマー酸及びトリマー酸由来の炭化水素基を示し、Ｂは独立して環状構造を含む４価の有機基を示し、ｎは１～１０００である。 (A) A maleimide compound represented by the following general formula (1): Component (A) is a maleimide compound represented by the following general formula (1).

In formula (1), A independently represents a hydrocarbon group derived from a dimer acid or trimer acid, B independently represents a tetravalent organic group containing a cyclic structure, and n is 1 to 1,000.

In formula (1), A is a hydrocarbon group derived from a dimer acid, and the proportion of the hydrocarbon groups derived from a dimer acid among the hydrocarbon groups derived from a dimer acid and a trimer acid is 95% by mass or more. Hereinafter, the proportion of the hydrocarbon groups derived from a dimer acid among the hydrocarbon groups derived from a dimer acid and a trimer acid may be simply referred to as the "dimer proportion" or dimer:trimer.
When the dimer ratio is 95% by mass or more, the maleimide compound of component (A) has low viscosity, excellent handleability of the compound itself, and when made into a composition, has advantages such as high moldability, etc. The dimer ratio is 95% by mass or more, preferably 96% by mass or more, more preferably 97% by mass or more, even more preferably 98% by mass or more, and particularly preferably 99% by mass or more.
Furthermore, A in formula (1) is a hydrogenated group. That is, as described below, the group corresponding to group A of the amine compound serving as the raw material of component (A) may contain a double bond, but this amine compound is hydrogenated to reduce the number of double bonds and used as the raw material. By reducing the number of double bonds in group A, oxidation of the double bonds is suppressed, and deterioration due to heat and the resulting deterioration of dielectric properties can be prevented.

In this specification, the dimer ratio is a value calculated from the peak area ratio in gas chromatography (GC) measurement carried out under the following measurement conditions.
Measurement conditions:
Equipment: GC-2014 (Shimadzu Corporation)
Column: DB-5 30m x 0.25mm x 0.25μm
Vaporization chamber temperature: 280°C
Temperature: 50° C. → 10° C./min → 300° C., held for 20 min. Column flow rate: 1.00 mL/min Purge flow rate: 3.00 mL/min

As mentioned above, dimer acid and trimer acid are generally mixtures, and are often referred to collectively as dimer acid. The same is true for dimer diamines and trimer triamines derived from dimer acid and trimer acid, which are collectively referred to as dimer diamines. It is well known that the ratio of dimer diamine and trimer triamine varies depending on the product, even among commercially available products of compounds called dimer diamines.

The dimer acid referred to here is a liquid dibasic acid mainly composed of a dicarboxylic acid having 36 carbon atoms, which is produced by dimerization of unsaturated fatty acids having 18 carbon atoms, which are made from natural products such as vegetable oils and fats, and dimer acids do not have a single skeleton but have multiple structures, and there are several types of isomers. Representative dimer acids are classified into linear (a), monocyclic (b), aromatic (c), and polycyclic (d).

（式（ｅ）中のＲはエチレン基又はエテニレン基を示す。） Trimer acid is a by-product of the production of dimer acid, and like dimer acid, trimer acid does not have a single structure but has multiple structures, and there are several types of isomers. A representative structure is shown in the following formula (e).

(In formula (e), R represents an ethylene group or an ethenylene group.)

（上記構造式中の置換基が結合していない結合手は、式（１）において環状イミド構造を形成するカルボニル炭素と結合するものである。） In formula (1), B independently represents a tetravalent organic group having a cyclic structure, and among these, any of the tetravalent organic groups represented by the following structural formulas is preferable.

(The bond not bonded to a substituent in the above structural formula is bonded to the carbonyl carbon that forms a cyclic imide structure in formula (1).)

In formula (1), n is 1 to 1000, preferably 1 to 100, and more preferably 3 to 50. This range is preferable because the resin composition has high strength even when uncured and also has good solvent solubility.

The component (A) used in the present invention can be produced using as a raw material a mixture of the dimer diamine derived from the dimer acid and the trimer triamine derived from the trimer acid (hereinafter referred to as a mixture of dimer diamine and trimer triamine). The dimer diamine derived from the dimer acid has a structure in which the two carboxy groups of the dimer acid are each replaced with a primary aminomethyl group, and similarly, the trimer triamine derived from the trimer acid has a structure in which the three carboxy groups of the trimer acid are each replaced with a primary aminomethyl group. Therefore, when A in formula (1) indicates a hydrocarbon group derived from a dimer acid and a trimer acid, it means that the group A is derived from a mixture of the dimer diamine derived from the dimer acid and the trimer triamine derived from the trimer acid.

The component (A) used in the present invention may be a commercially available product such as BMI-1500 or BMI-3000 (both manufactured by Designer Molecules Inc.), or may be synthesized by the following method.

A specific example of a method for producing the component (A) is to react a mixture of dimer diamine and trimer triamine with a tetracarboxylic dianhydride having a cyclic structure and maleic anhydride.
This reaction can be carried out in accordance with a known method for synthesizing polyimide, in which an amic acid is synthesized from a diamine and a carboxylic anhydride, and the amic acid is dehydrated. That is, an example of a method is to synthesize an amic acid from a mixture of a dimer diamine and a trimer triamine and a tetracarboxylic dianhydride having a cyclic structure, and then ring-closing and dehydrating the amic acid, and then reacting the mixture with maleic anhydride to synthesize maleamic acid and ring-closing and dehydrating the amic acid. The reaction for synthesizing (maleic)amic acid generally proceeds at room temperature (25°C) to 100°C in an organic solvent (e.g., a non-polar solvent or a high-boiling aprotic polar solvent). The subsequent ring-closing and dehydration reaction of the amic acid proceeds while removing water by-produced by the condensation reaction from the system after the reaction under conditions of 90 to 120°C. In order to promote the ring-closing and dehydration reaction, an organic solvent (e.g., a non-polar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst may be added. Examples of the organic solvent include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. These may be used alone or in combination of two or more. Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. These may be used alone or in combination of two or more.
The molar ratio of the tetracarboxylic dianhydride having a cyclic structure to the mixture of dimer diamine and trimer triamine is preferably tetracarboxylic dianhydride having a cyclic structure/mixture of dimer diamine and trimer triamine=0.5 to 0.999/1.0.
The maleic anhydride added thereafter is preferably added in an amount such that the ratio of maleic anhydride/mixture of dimer diamine and trimer triamine becomes 0.1 to 10.0/1.0.

In the above reaction, the ratio of the raw materials dimer diamine and trimer triamine in the mixture and the presence or absence of hydrogenation are directly reflected in the obtained maleimide compound, and therefore, from the viewpoint of productivity, it is preferable to use a mixture of the raw materials dimer diamine and trimer triamine having a dimer ratio of 95 mass% or more and having been hydrogenated. Examples of such a mixture of dimer diamine and trimer triamine include the following commercially available products.

Versamine 552 (manufactured by Cognics Japan Co., Ltd.), dimer:trimer=95:5, hydrogenated Priamine-1075 (manufactured by Croda Japan Co., Ltd.), dimer:trimer=98:2, hydrogenated

The above-mentioned commercial products or other commercial products of mixtures of dimer diamine and trimer triamine may be used with the dimer ratio increased by a purification method such as thin film distillation, or a mixture of multiple types of dimer diamine and trimer triamine with different dimer ratios may be combined to adjust the dimer ratio. Also, a commercial product of a mixture of dimer diamine and trimer triamine that has not been hydrogenated may be hydrogenated using a catalyst such as Raney nickel.

As the tetracarboxylic acid anhydride having a cyclic structure, commercially available products can be used, such as pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and the like. These acid anhydrides may be used alone or in combination with two or more types depending on the purpose and application. From the viewpoint of the electrical properties of the maleimide compound, the acid anhydride is preferably pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, or 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride.

In order to reduce warpage when the composition of the present invention is cured, the storage modulus of the cured product of the composition at 25° C. is preferably less than 1000 MPa, more preferably 900 MPa or less, and even more preferably 800 MPa or less. If the storage modulus is 1000 MPa or more, warpage after curing may be significant when the composition is used as an adhesive or film.
The storage modulus is a value measured in accordance with the method described in JIS K7244-4:1999 using a dynamic viscoelasticity measuring device, for example, a DMA-Q800 (manufactured by TA Instruments), under the measurement conditions of a frequency of 10 Hz, a temperature range of −50° C. to 200° C., and a heating rate of 5° C./min.

In order to improve the crack resistance of the cured product of the composition of the present invention, the hardness of the cured product at 25°C is preferably D50 or less, more preferably D40 or less, and even more preferably D30 or less. If the hardness is greater than D50, the crack resistance may be poor when used as a semiconductor encapsulant. The hardness is a value measured at 25°C using a durometer type D hardness tester in accordance with the method described in JIS K 6253-3:2012.

The component (A) may be used alone or in combination of two or more types.
The content of the component (A) in the curable resin composition of the present invention is preferably from 30 to 99 mass %, and more preferably from 60 to 95 mass %.

(B) Catalyst The (B) component used in the present invention is a catalyst. The catalyst in the present invention initiates or accelerates the reaction of the maleimide group of the (A) component and/or a group reactive with the maleimide group described below. The (B) component is not particularly limited as long as it initiates or accelerates the reaction of the maleimide group of the (A) component and/or a group reactive with the maleimide group described below, but at least one selected from an organic peroxide, an anionic polymerization initiator, and a photocuring initiator is preferably used.

Examples of organic peroxides include dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, dibenzoyl peroxide, diuraroyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, di-t-butyl peroxide, and dibenzoyl peroxide.

Examples of anionic polymerization initiators include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole. imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphorus compounds such as tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine, triphenylphosphine oxide, triphenylphosphine-triphenylborane, and tetraphenylphosphine-tetraphenylborate; and tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo[5.4.0]undecene, and tris(dimethylaminomethyl)phenol.

There are no particular limitations on the photocuring initiator as long as it initiates a reaction by light, but examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, and phenanthrenequinone. Aromatic ketones; benzil derivatives such as benzil dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl) 2,4,5-triarylimidazole dimers such as 2-(2,4-dimethoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; bisacyl derivatives such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Phosphine oxides; alkylphenone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; benzophenone compounds, etc.

The amount of component (B) blended is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.5 parts by mass, and even more preferably 0.5 to 4.0 parts by mass, per 100 parts by mass of component (A).
Furthermore, when the composition of the present invention contains a curable resin having a reactive group capable of reacting with a maleimide group other than the component (A) described below, the total of the component (A) and the curable resin having a reactive group capable of reacting with a maleimide group is defined as the curable resin component, and the blending amount of the component (B) is preferably 0.1 to 7.0 parts by mass, more preferably 0.2 to 6.0 parts by mass, and even more preferably 0.5 to 5.0 parts by mass relative to 100 parts by mass of the curable resin component.
If the amount of component (B) is less than 0.1 parts by mass per 100 parts by mass of component (A), the curing process may proceed slowly, whereas if it is more than 5.0 parts by mass, the composition may lack storage stability.
The component (B) may be used alone or in combination of two or more.

Other Additives Various additives may be further blended into the curable resin composition of the present invention as necessary within the range not impairing the effects of the present invention. Examples of other additives are listed below.

Curable resin having a reactive group capable of reacting with a maleimide group In the present invention, a curable resin having a reactive group capable of reacting with a maleimide group may be further added.
The type of the curable resin is not limited, and examples thereof include various resins other than component (A), such as epoxy resins, phenol resins, melamine resins, silicone resins, cyclic imide resins including maleimide compounds other than component (A), urea resins, thermosetting polyimide resins, modified polyphenylene ether resins, (meth)acrylic resins, and epoxy-silicone hybrid resins. Examples of reactive groups that can react with maleimide groups include epoxy groups, maleimide groups, hydroxyl groups, acid anhydride groups, alkenyl groups such as allyl groups and vinyl groups, (meth)acrylic groups, and thiol groups.

From the viewpoint of reactivity, the reactive group of the curable resin is preferably selected from among an epoxy group, a maleimide group, a hydroxyl group, and an alkenyl group, and from the viewpoint of dielectric properties, an alkenyl group or a (meth)acrylic group is more preferable.
However, the blending amount of the curable resin having a reactive group capable of reacting with a maleimide group is 0 to 80 mass % in the total amount of the curable resin.

Inorganic filler In the present invention, an inorganic filler may be added as necessary. The inorganic filler is blended for the purpose of increasing the strength or rigidity of the cured product of the curable resin composition of the present invention, or adjusting the thermal expansion coefficient or dimensional stability of the cured product. As the inorganic filler, those usually blended in epoxy resin compositions or silicone resin compositions can be used. For example, silicas such as spherical silica, fused silica, and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, barium sulfate, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fiber, and glass particles can be mentioned. Furthermore, fluorine-containing resins, coating fillers, and/or hollow particles may be used to improve dielectric properties, and conductive fillers such as metal particles, metal-coated inorganic particles, carbon fibers, and carbon nanotubes may be added for the purpose of imparting conductivity. The inorganic filler may be used alone or in combination of two or more types. The amount of inorganic filler added may be 0 to 300 parts by mass relative to 100 parts by mass of component (A), and preferably 30 to 300 parts by mass.

The average particle size and shape of the inorganic filler are not particularly limited, but when molding a film or substrate, spherical silica having an average particle size of 0.5 to 5 μm is preferably used. The average particle size is the value determined as the mass average value _D50 (or median diameter) in particle size distribution measurement by laser light diffraction method.

Furthermore, in order to improve the properties of the inorganic filler, it is preferable that the inorganic filler is surface-treated with a silane coupling agent having an organic group capable of reacting with a maleimide group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane, amino group-containing alkoxysilane, (meth)acrylic group-containing alkoxysilane, and alkenyl group-containing alkoxysilane.
As the silane coupling agent, a (meth)acrylic group- and/or amino group-containing alkoxysilane is suitably used, and specific examples thereof include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.

There are no particular limitations on the amount of the silane coupling agent used, but it should be 0 to 5 parts by mass, and preferably 0.2 to 2 parts by mass, per 100 parts by mass of the inorganic filler added.

Others In addition to the above, non-functional silicone oils, reactive diluents, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, photosensitizers, light stabilizers, polymerization inhibitors, antioxidants, flame retardants, pigments, dyes, adhesion aids, ion trapping materials, etc. may be blended.
In addition, a silane coupling agent such as an epoxy group-containing alkoxysilane, an amino group-containing alkoxysilane, a (meth)acrylic group-containing alkoxysilane, or an alkenyl group-containing alkoxysilane, which is used to surface treat the above-mentioned inorganic filler, may be separately blended into the curable resin composition of the present invention, and specific examples thereof include the same as those described above.

The curable resin composition of the present invention can be dissolved in an organic solvent and treated as a varnish. By making the composition into a varnish, it becomes easier to form a film, and it is also easier to apply and impregnate a fiber substrate such as glass cloth made of E-glass, low dielectric glass, quartz glass, etc. Regarding organic solvents, any organic solvent that dissolves the curable resin having a reactive group that can react with the maleimide group as the component (A) and the component (B) and other additives can be used without restriction. Examples of the organic solvents include anisole, tetralin, mesitylene, xylene, toluene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, etc. These may be used alone or in combination of two or more.

[Manufacturing method]
Examples of a method for producing the curable resin composition of the present invention include a method in which the components (A) and (B) and other additives added as necessary are mixed using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a mixer such as a THINKY CONDITIONING MIXER (manufactured by Thinky Corporation).

[Uncured resin film/cured resin film]
The curable resin composition of the present invention can be made into an uncured resin sheet or an uncured resin film by applying the above-mentioned varnish to a substrate and volatilizing the organic solvent, and can be made into a cured resin sheet or a cured resin film by curing the uncured resin sheet or the cured resin film. Examples of the manufacturing method of the sheet and the film are shown below, but are not limited thereto.

For example, a curable resin composition (varnish) dissolved in an organic solvent is applied to a substrate, and then the organic solvent is removed by heating for 0.5 to 20 minutes at a temperature of usually 80° C. or higher, preferably 100° C. or higher, and then further heating for 0.5 to 10 hours at a temperature of 130° C. or higher, preferably 150° C. or higher, to form a strong cured resin coating having a flat surface.
The temperatures in the drying step for removing the organic solvent and the subsequent heat curing step may each be constant, but it is preferable to increase the temperature stepwise, which allows the organic solvent to be efficiently removed from the composition and allows the curing reaction of the resin to proceed efficiently.
The method for applying the varnish includes, but is not limited to, a spin coater, a slit coater, a spray, a dip coater, a bar coater, and the like.

As the substrate, a general resin substrate can be used, for example, polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, and polystyrene (PS) resin, and polyester resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, and polycarbonate (PC) resin. The surface of the substrate may be subjected to a release treatment. The thickness of the coating layer is not particularly limited, but the thickness after distillation of the solvent is in the range of 1 to 100 μm, preferably 3 to 80 μm. Furthermore, a cover film may be used on the coating layer.

Alternatively, the components may be premixed and extruded into a sheet or film using a melt kneader to produce an uncured or cured resin film.

The cured film obtained by curing the curable resin composition of the present invention has excellent heat resistance, mechanical properties, electrical properties, adhesion to substrates, and solvent resistance, and also has a low dielectric constant. Therefore, it can be applied to, for example, semiconductor devices, specifically, passivation films and protective films on the surface of semiconductor elements, junction protective films for junctions of diodes and transistors, alpha-ray shielding films for VLSIs, interlayer insulating films, ion implantation masks, etc., as well as conformal coats for printed circuit boards, alignment films for liquid crystal surface elements, protective films for glass fibers, and surface protective films for solar cells. Furthermore, it can be applied to a wide range of paste compositions, such as a printing paste composition in which an inorganic filler is blended with the curable resin composition, and a conductive paste composition in which a conductive filler is blended. Among these, adhesive applications are preferred.

In addition, it can be made into a film or sheet in an uncured state, and has self-adhesive properties and excellent dielectric properties, making it particularly suitable for use as a bonding film for flexible printed circuit boards (FPCs) and as an interlayer insulating material for rigid substrates. The cured resin film can also be used as a coverlay film.

In addition, the varnished curable resin composition can be used as a prepreg by impregnating a fiber substrate such as glass cloth made of E-glass, low dielectric glass, or quartz glass, removing the organic solvent, and semi-curing the substrate. In addition, laminates and printed wiring boards, including those with high multilayers, can be produced by laminating the prepreg and copper foil.

[Prepreg]
A schematic end view of a prepreg according to one embodiment of the present invention is shown in Fig. 1. The prepreg 1 includes a curable resin composition 2 and a fiber base material 3. The curable resin composition 2 is the curable resin composition or a semi-cured product of the resin composition.
The term "semi-cured product" refers to a resin composition that has been partially cured to such an extent that it can be further cured. In other words, the semi-cured product refers to a resin composition that has been semi-cured, or in other words, in the B stage. On the other hand, the uncured state is sometimes called the A stage.
That is, the curable resin composition 2 may be the curable resin composition in an A-stage state, or may be the curable resin composition in a B-stage state.

As mentioned above, the fiber substrate 3 can be E-glass, low dielectric glass, quartz glass, S-glass, T-glass, etc., and the type of glass used is not important, but quartz glass cloth, which has low dielectric properties, is preferred from the viewpoint of taking advantage of the properties of the curable resin composition. The thickness of the fiber substrate that is generally used is, for example, 0.01 mm or more and 0.3 mm or less.

When producing the prepreg 1, the curable resin composition 2 is preferably prepared as a resin varnish in a varnish form in order to impregnate the fiber base material 3, which is a base material for forming the prepreg. Such a varnish-like resin composition (resin varnish) is prepared, for example, as follows.
First, each component of the resin composition that can be dissolved in an organic solvent is put into the organic solvent and dissolved. At this time, heating may be performed as necessary. Then, a component that is not dissolved in an organic solvent, such as an inorganic filler, is added as necessary, and dispersed until a predetermined dispersion state is reached using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like, to prepare a varnish-like resin composition (resin varnish). The organic solvent used here is not particularly limited as long as it does not inhibit the curing reaction. Specific examples include toluene, methyl ethyl ketone (MEK), xylene, and anisole.

As a method for producing the prepreg 1, for example, a method of impregnating the fiber substrate 3 with the curable resin composition 2, for example, the curable resin composition 2 prepared in a varnish form, and then drying the same can be mentioned. The curable resin composition 2 is impregnated into the fiber substrate 3 by immersion, coating, etc. It is also possible to repeat the impregnation several times as necessary. In addition, at this time, it is also possible to adjust to the desired composition and impregnation amount by repeating the impregnation using several resin compositions with different compositions and concentrations. The fiber substrate 3 impregnated with the curable resin composition (resin varnish) 2 is heated under the desired heating conditions, for example, at 80°C or higher and 180°C or lower for 1 minute or longer and 20 minutes or shorter. By heating, a prepreg 1 having the curable resin composition 2 in a pre-cured (A stage) or semi-cured (B stage) state can be obtained. In addition, the organic solvent can be volatilized from the resin varnish by the heating, and the organic solvent can be reduced or removed.

[Laminate]
The laminate according to one embodiment of the present invention is a laminate in which an insulating layer containing a cured product of the curable resin composition or an insulating layer made of a cured product of the curable resin composition is laminated with a layer other than the insulating layer. A commonly known laminate is a metal-clad laminate, and a schematic end view thereof is shown in FIG. 2. The metal-clad laminate 11 includes an insulating layer 12 containing or made of a cured product of the curable resin composition, and metal foils 13 on both sides of the insulating layer 12. Although FIG. 2 illustrates a double-sided metal-clad laminate having metal foils 13 on both sides of the insulating layer 12, the laminate may be a single-sided metal-clad laminate having metal foils 13 only on one side of the insulating layer 12.
The insulating layer 12 may be made of a cured product of the curable resin composition, may be made of a cured product of the prepreg, or may be made by laminating a plurality of cured products of the prepreg 1. The thickness of the metal foil 13 varies depending on the performance required for the final wiring board, and is not particularly limited. The thickness of the metal foil 13 can be appropriately set depending on the desired purpose, and is preferably, for example, 1 to 70 μm. Examples of the metal foil 13 include copper foil and aluminum foil, and when the metal foil is thin, it may be a carrier-attached copper foil having a release layer and a carrier to improve handling properties.
The method for producing such a laminate is not particularly limited as long as it is a general method. For example, when a prepreg is used, a laminate can be produced by stacking one or more prepregs 1 (FIG. 1), stacking a metal foil 13 such as a copper foil on either or both sides of the prepreg 1, and then heating and pressing the stacked sheets to form an integrated laminate.

[Printed wiring board]
The printed wiring board according to one embodiment of the present invention contains a cured product of the curable resin composition, and as an example thereof, a schematic end view of a printed wiring board manufactured using the laminate, particularly the metal-clad laminate shown in FIG. 2, is shown in FIG. 3. As described above, the insulating layer 12 of the metal-clad laminate used in the manufacture of the printed wiring board may be manufactured using the prepreg described above. The printed wiring board 21 can be manufactured by performing a circuit formation process and a multi-layer adhesive process by a known method, such as drilling, metal plating, and etching of metal foil.

[Semiconductor encapsulation material]
When the curable resin composition of the present invention is used as a semiconductor encapsulant, the components (A) and (B) and, if necessary, other components are blended in a predetermined composition ratio, thoroughly and uniformly mixed with a mixer or the like, then melt-mixed with a hot roll, kneader, extruder, etc., and then cooled and solidified, and pulverized to an appropriate size. The resulting resin composition can be used as an encapsulant.

Examples of typical molding methods for semiconductor encapsulation materials include transfer molding and compression molding. In the transfer molding method, a transfer molding machine is used, and molding pressure is 5 to 20 N/mm ² , molding temperature is 120 to 190° C., molding time is 30 to 500 seconds, preferably molding temperature is 150 to 185° C., molding time is 30 to 180 seconds. In the compression molding method, a compression molding machine is used, and molding temperature is 120 to 190° C., molding time is 30 to 600 seconds, preferably molding temperature is 130 to 160° C., molding time is 120 to 300 seconds. In addition, in either molding method, post-curing may be performed at 150 to 225° C. for 0.5 to 20 hours.

The present invention will be specifically explained below with examples and comparative examples, but the present invention is not limited to the following examples.

The components used in the examples and comparative examples are shown below. In the following, the number average molecular weight (Mn) was measured under the following measurement conditions using polystyrene as the standard.
[Measurement conditions]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Refractive index detector (RI)
Column: TSK Guard column Super H-L
TSKgel SuperHZ4000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL (THF solution with a concentration of 0.2% by mass)

The dimer ratio (mass ratio of dimer:trimer) was calculated from the peak area ratio in gas chromatography (GC) measurement performed under the following measurement conditions.
[Measurement conditions]
Equipment: GC-2014 (Shimadzu Corporation)
Column: DB-5 30m x 0.25mm x 0.25μm
Vaporization chamber temperature: 280°C
Temperature: 50° C. → 10° C./min → 300° C., held for 20 min. Column flow rate: 1.00 mL/min Purge flow rate: 3.00 mL/min

Amine Compounds In the synthesis examples, amine compounds obtained by the following procedures or commercially available amine compounds were used.
[Amine compound 1]
Priamine-1075 (manufactured by Croda Japan Co., Ltd., hydrogenated, dimer:trimer ≒ 98:2)
[Amine compound 2]
Priamine-1074 (manufactured by Croda Japan Co., Ltd., hydrogenated, dimer:trimer ≒ 95:5)
[Amine compound 3]
300 g of Priamine-1075 was subjected to thin-film distillation at 200° C. for 60 minutes to obtain amine compound 3. The main chain of amine compound 3 was hydrogenated, and the ratio of dimer:trimer was approximately 99.2:0.8.
[Amine compound 4]
A mixture of 80 g of Priamine-1075 and 161 g of Priamine-1074 was obtained as amine compound 4. The main chain of amine compound 4 was hydrogenated, and the ratio of dimer:trimer was approximately 96:4.
[Amine Compound 1' (for Comparative Example)]
Priamine-1073 (manufactured by Croda Japan Co., Ltd., not hydrogenated, dimer:trimer ≒ 95:5)
[Amine compound 2' (for comparison)]
Priamine-1071 (manufactured by Croda Japan Co., Ltd., not hydrogenated, dimer:trimer ≒ 80:20)
[Amine Compound 3' (for Comparative Example)]
300 g of Priamine-1071 was subjected to thin-film distillation at 180° C. for 60 minutes, and then hydrogenated with Raney nickel to obtain amine compound 3′. The main chain of amine compound 3′ was hydrogenated, and the ratio of dimer:trimer was approximately 93:7.

(A) Maleimide Compound Using the amine compound as a raw material, a maleimide compound was synthesized by the following operation. Note that, in the maleimide compound obtained in each synthesis example, A in formula (1) is a hydrocarbon group derived from a dimer acid and a trimer acid, has a dimer ratio shown in Table 1, the presence or absence of hydrogenation of group A is also shown in Table 1, and B in formula (1) is a tetravalent organic group having a cyclic structure derived from the tetracarboxylic acid anhydride of each synthesis example.

[Synthesis Example 1]
A 1L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser and a thermometer was charged with 241 g (0.45 mol) of amine compound 1, 87 g (0.4 mol) of pyromellitic anhydride, 20 g of methanesulfonic acid and 300 g of toluene, and the mixture was heated to 110 ° C. and stirred for 24 hours while distilling off the by-produced water. After the reaction, 97 g (0.99 mol) of maleic anhydride was added, and the mixture was stirred for 6 hours while distilling off the by-produced water at 110 ° C., and the reaction solution was washed five times with 200 g of ion-exchanged water. Thereafter, 300 g of the target product (A-1) was obtained as a yellow solid by reprecipitation in hexane (yield 90%, Mn = 5000, n = 7 in formula (1)).

[Synthesis Example 2]
In a 1L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser and a thermometer, 428 g (0.8 mol) of amine compound 1, 186 g (0.6 mol) of 4,4'-oxydiphthalic anhydride, 20 g of methanesulfonic acid and 200 g of toluene were added, and the mixture was heated to 110°C and stirred for 24 hours while distilling off the by-produced water. After the reaction, 97.2 g (0.99 mol) of maleic anhydride was added, and the mixture was stirred for 6 hours at 110°C while distilling off the by-produced water, and the reaction solution was washed five times with 200 g of ion-exchanged water. Thereafter, 540 g (yield 87%, Mn = 3000, n = 3 in formula (1)) of the target product (A-2) was obtained as a brown solid at room temperature by vacuum stripping at 80°C.

[Synthesis Example 3]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 1 was replaced with an equimolar amount of amine compound 2, thereby obtaining 290 g (yield 88%, Mn=5,300, n=7 in formula (1)) of the target product (A-3) as a yellow solid.

[Synthesis Example 4]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 1 was replaced with an equimolar amount of amine compound 3, thereby obtaining 280 g (yield 85%, Mn=4500, n=6 in formula (1)) of the target product (A-4) as a yellow solid.

[Synthesis Example 5]
The same procedure was carried out as in Synthesis Example 1, except that 241 g of amine compound 1 was replaced with 241 g of amine compound 4, to obtain 290 g of the target product (A-5) as a yellow solid (yield 88%, Mn=5000, n=7 in formula (1)).

[Synthesis Example 6]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 2 was replaced with an equimolar amount of amine compound 3, thereby obtaining 530 g (yield 86%, Mn=3000, n=3 in formula (1)) of the target product (A-6) as a brown solid.

[Comparative Synthesis Example 1]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 1 was replaced with an equimolar amount of amine compound 1', thereby obtaining 290 g of the target product (A'-1) as a yellow solid (yield 88%, Mn = 6000, n in formula (1) = 8, for comparative example).

[Comparative Synthesis Example 2]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 1 was replaced with an equimolar amount of amine compound 2', thereby obtaining 300 g of the target product (A'-2) as a yellow solid (yield 90%, Mn = 7000, n in formula (1) = 9, for comparative example).

[Comparative Synthesis Example 3]
The same procedure was followed except that the amine compound 1 in Synthesis Example 1 was replaced with an equimolar amount of amine compound 3', thereby obtaining 290 g of the target product (A'-3) as a yellow solid (yield 88%, Mn = 7000, n in formula (1) = 9, for comparison).

[Comparative Synthesis Example 4]
The same procedure was carried out except that the amine compound 1 in Synthesis Example 2 was replaced with an equimolar amount of amine compound 2', thereby obtaining 530 g of the target product (A'-4) as a brown solid (yield 86%, Mn = 4000, n in formula (1) = 4, for comparative example).

(B) Catalyst (B-1): 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (product name: Trigonox 101, manufactured by Kayaku Nouryon Co., Ltd.)

<Sample preparation>
The components were placed in a plastic container in the blending ratios shown in Table 2 and mixed using a Thinky Mixer (manufactured by Thinky Corporation, product name: Awatori Rentaro ARE-310) to prepare each resin composition.

<Storage modulus>
A 50 mm x 50 mm, 1 mm thick frame was prepared, and each resin composition was sandwiched between two 50 μm thick release-treated PET films (E7006, manufactured by Toyobo), and molded using a vacuum press (manufactured by Nikko Materials) at 160 ° C for 5 minutes to produce a cured product. The produced cured product was cut into a size of 20 mm long x 5 mm wide x 1 mm thick, and the storage modulus at 25 ° C was measured using a dynamic viscoelasticity measuring device DMA-Q800 (manufactured by TA Instruments) at a temperature range of -50 ° C to 200 ° C, a frequency of 10 Hz, and a heating rate of 5 ° C / min.

<Hardness>
Each prepared resin composition was poured into an aluminum petri dish having a diameter of 50 mm and a thickness of 10 mm, and molded at 160° C. for 5 minutes to produce a cured product. The hardness of the obtained cured product was measured at 25° C. using a durometer type D hardness tester in accordance with the method described in JIS K 6253-3:2012.

<Warpage characteristics>
Each prepared resin composition was coated in a film shape of 350 mm x 350 mm and 100 μm thick. The coated film was laminated on a silicon wafer of 300 mm diameter and 750 μm thickness using a film laminator V-100 (manufactured by Nikko Materials), and heated at 160 ° C for 5 minutes to prepare a cured product on the silicon wafer. After cooling the prepared cured product to 25 ° C, one end of the silicon wafer was fixed to a desk, and the distance (height) from the desk to the other end of the silicon wafer that was not fixed was measured, and if the height was 5 mm or less, it was judged as good, and if it was greater than 5 mm, it was judged as bad.

<Crack resistance>
A 32mm x 32mm, 1.6mm thick glass epoxy printed wiring board was prepared with a 10mm x 10mm, 0.75mm thick silicon chip mounted thereon, and transfer molded at 160°C, 6.9N/ ^mm2 , and 5 minutes curing time to produce a semiconductor device with a molded size of the curable resin of 28 x 28mm and a molded thickness of 1.2mm. Twenty of the produced semiconductor devices were subjected to thermal cycle tests (TCT) of -40°C/30min, 150°C/30min, and 1,000 cycles, respectively, and the number of semiconductor devices in which cracks occurred in the curable resin was counted.

<Dielectric properties and heat resistance>
A 70 mm x 70 mm, 200 μm thick frame was prepared, and each resin composition was sandwiched between two 50 μm thick release-treated PET films (E7006, manufactured by Toyobo), and molded at 160 ° C. for 5 minutes using a vacuum press (manufactured by Nikko Materials) to produce a cured product (molded film). The molded film was post-cured at 180 ° C. for 1 hour to obtain a cured resin film, and then the cured resin film was used to connect a network analyzer (manufactured by Keysight, product name: E5063-2D5) and a strip line (manufactured by Keycom Co., Ltd.) to measure the relative dielectric constant and dielectric loss tangent of the cured resin film at frequencies of 10 GHz and 28 GHz.
Furthermore, this cured resin film was left to stand at 150° C. for 48 hours, and the relative dielectric constant and dielectric loss tangent of the cured resin film were similarly measured at frequencies of 10 GHz and 28 GHz.

From the above, it was found that the cured product of the composition of the present invention has low elasticity and low hardness, so that it warps little after curing, has excellent crack resistance, exhibits excellent dielectric properties even at high frequencies, and shows little change in dielectric properties even after being left at high temperatures for long periods of time.

Reference Signs List 1 Prepreg 2 Curable resin composition 3 Fiber base material 11 Metal-clad laminate 12 Insulating layer 13 Metal foil 21 Printed wiring board 22 Wiring layer

Claims (9)

(A) A maleimide compound represented by the following general formula (1):

(In formula (1), A independently represents a hydrocarbon group derived from a dimer acid or a trimer acid, B independently represents a tetravalent organic group containing a cyclic structure, and n is 1 to 1,000.)
and (B) a catalyst,
The content of the component (A) in the curable resin composition is 60 to 99 mass %,
A curable resin composition for semiconductor encapsulation, wherein A in formula (1) is a group in which the proportion of hydrocarbon groups derived from a dimer acid and a trimer acid is 95 mass% or more, and which has been hydrogenated. The curable resin composition according to claim 1, wherein the storage modulus of the cured product of the curable resin composition is less than 1000 MPa, as measured at a measurement temperature of 25°C using a dynamic viscoelasticity measuring device at a frequency of 10 Hz, in a temperature range of -50°C to 200°C, and at a heating rate of 5°C/min, in accordance with the method described in JIS K7244-4:1999. The curable resin composition according to claim 1, wherein the hardness of the cured product of the curable resin composition is D50 or less, measured using a durometer type D hardness tester at a measurement temperature of 25°C according to the method described in JIS K 6253-3:2012. The curable resin composition according to claim 1, wherein the catalyst of component (B) is at least one selected from an organic peroxide, an anionic polymerization initiator, and a photocuring initiator. An adhesive comprising the curable resin composition according to any one of claims 1 to 4. An adhesive film made of the curable resin composition according to any one of claims 1 to 4. A prepreg comprising the curable resin composition according to any one of claims 1 to 4 and a fiber substrate. An interlayer insulating material comprising the curable resin composition according to any one of claims 1 to 4. A printed wiring board having a cured product of the curable resin composition according to any one of claims 1 to 4.