Compound, curable resin composition and cured product thereof, and method for producing compound

Abstract

The present application provides a compound having excellent solvent stability and low dielectric properties, a curable resin composition, and a cured product thereof. The compound of the present application is a compound represented by the following formula (1), wherein the compound of formula (1) in which n is 1 is not more than 50% by GPC area percentage in the total amount of the aforementioned compound. (In formula (1), each of the plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p and r are integers of 0 to 4, and q is an integer of 0 to 3. n is the number of repetitions, and the average value of n is n ave satisfies 1 ≤ n ave ≤ 20.)

Description

TECHNICAL FIELD

[0001] The present application relates to a compound, a curable resin composition and a cured product thereof, and a manufacturing method of the compound, which are suitable for use in electrical and electronic components such as semiconductor sealing materials, printed wiring boards, build-up laminated boards, lightweight high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications. BACKGROUND

[0002] In recent years, as the application fields of laminated boards on which electrical and electronic components are mounted expand, the required characteristics have become more extensive and highly sophisticated. In the past, semiconductor chips were mainly mounted on lead frames made of metal, but high-performance semiconductor chips such as central processing units (hereinafter referred to as CPUs) are increasingly mounted on laminated boards made of high molecular materials.

[0003] In particular, semiconductor packages (hereinafter referred to as PKGs) used in smartphones and the like are required to have a thinner thickness of the PKG substrate in order to meet the requirements of miniaturization, thinness, and high density, but the thinner the PKG substrate, the lower the rigidity, and thus problems such as large warping due to heat generation occur when the PKG solder is mounted to a mother board (printed circuit board: PCB). In order to reduce such cases, a PKG substrate material having a high Tg above the solder mounting temperature is required.

[0004] In addition, in the 5th generation communication system "5G" that is being developed at an accelerated pace, further improvement in capacity and high-speed communication is expected. There is an increasing demand for low dielectric loss tangent materials, and various studies are being conducted. Patent Document 1 describes a heat-curable resin composition in which (A) an imine compound having a maleimide group and (B) a phenol aralkyl resin having an aliphatic unsaturated bond in one molecule are essential components. Patent Document 2 describes an allyl ether-modified biphenyl aralkyl novolak resin. Patent Document 3 describes a compound having a styrene structure.

[0005] [Related Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 04-359911

[0008] [Patent Document 2] International Publication No. 2016 / 002704

[0009] [Patent Document 3] Japanese Patent No. 6951829. SUMMARY

[0010] [Problems to be Solved by the Invention]

[0011] When the applicant of the present application retested Patent Document 3, it was found that when synthesized by the method described in Patent Document 3, there was a problem of crystallization when the synthesized compound was stored in a state of being dissolved in a solvent such as toluene. In order to solve this problem of crystallization, the use of a compound precursor having a 2-bromoethylbenzene structure with a high molecular weight was also investigated, but in this case, the problem that the polymerization reaction of the styrene side could not be completely performed occurred. Furthermore, the reaction conditions were also investigated to be made more severe in order to promote the reaction, but although the progress rate (conversion rate) of the reaction increased, the increase in impurities lowered the electrical characteristics, and the progress of an unexpected radical polymerization reaction occurred, and other problems such as a high molecular weight and gelation occurred. That is, it was extremely difficult to simultaneously achieve solvent stability and the suppression of impurity generation (low dielectric characteristics).

[0012] The present application was made in view of such a situation, and aims to provide a compound having excellent solvent stability, low dielectric characteristics, a curable resin composition and a cured product thereof, and a method for producing the compound.

[0013] [Means for solving the problem]

[0014] That is, the present application relates to the following [1] to

[13] . [1]

[0016] A compound represented by the following formula (1) in which, in the total amount of the aforementioned compound, the compound in which n in formula (1) is 1 is not more than 50% by GPC area percentage.

[0017]

[0018] (In formula (1), the plurality of R's each independently represent a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. p, r are integers of 0 to 4, q is an integer of 0 to 3, n is the number of repetitions, and the average value of n is n ave 1≤n ave ≤20.) [2]

[0020] The compound described in the preceding [1], in which the sum (a) of the peak areas of HP-LC of the compounds represented by the following formulas (2) to (4) is 0.10 or less with respect to the value (a / b) of the peak area (b) of HP-LC of the compound in which n in the aforementioned formula (1) is 1.

[0021]

[0022] (In formula (2), the plurality of R's each independently represent a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. The plurality of s's each independently are integers of 0 to 4.)

[0023]

[0024] (In formula (3), each of the plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. Each of the plurality of A's is independently any one of the following formulae (3-a) to (3-c). Each of the plurality of s' s is independently an integer of 0 to 4, and t is an integer of 0 to 3.)

[0025]

[0026] (In formulae (3-a) to (3-c), * indicates a position bonded to the aromatic ring of the compound of formula (3).)

[0027]

[0028] (In formula (4), each of the plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. Each of the plurality of B's is independently formula (4-d) or (4-e) below. D is formula (4-f) below. Each of the plurality of s' s is independently an integer of 0 to 4, and t is an integer of 0 to 3. One of the five m's in formula (4) is 1, and the remaining four are 0.)

[0029]

[0030] (In formulae (4-d) to (4-f), * indicates a position bonded to the aromatic ring of the compound of formula (4).) [3]

[0032] The compound according to any one of the preceding [1] or [2], wherein, in the aforementioned formula (1), p = 0, q = 0, and r = 0. [4]

[0034] The compound according to any one of the preceding [1] to [3], wherein the compound represented by the aforementioned formula (1) is derived from a compound represented by the following formula (5).

[0035]

[0036] (In formula (5), each of the plurality of R's is present and represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p and r are integers of 0 to 4, q is an integer of 0 to 3, n is a repetition number, and the average value of n is n ave satisfying 1 ≤ n ave ≤ 20. X represents a halogen atom.) [5]

[0038] The mixture according to any one of the preceding [1] to [4] further contains a polymerization inhibitor. [6]

[0040] A curable resin composition containing the compound according to any one of the preceding [1] to [4], or the mixture according to the preceding [5]. [7]

[0042] The curable resin composition according to the preceding [6], containing any one or more of a polyphenylene ether compound, a polybutadiene and a modified product thereof, and a polystyrene and a modified product thereof. [8]

[0044] The curable resin composition according to the preceding [6] or [7], containing a radical polymerization initiator. [9]

[0046] A cured product obtained by curing the compound according to any one of the preceding [1] to [4], the mixture according to the preceding [5], or the curable resin composition according to any one of the preceding [6] to [8].

[10]

[0048] A production method of a compound represented by the following formula (1), wherein a compound represented by the following formula (5) is subjected to a dehydrohalogenation reaction in a solvent of 4 to 7 times by weight of the compound represented by the formula (5) in the presence of a basic catalyst.

[0049]

[0050] (In the formula (1), R present in plurality is present independently and represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p, r are integers of 0 to 4, q is an integer of 0 to 3, n is a repeating number, and the average value n of n ave satisfies 1 ≤ n ave ≤ 20.)

[0051]

[0052] (In the formula (5), R present in plurality is present independently and represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p, r are integers of 0 to 4, q is an integer of 0 to 3, n is a repeating number, and the average value n of n ave satisfies 1 ≤ n ave ≤ 20. X represents a halogen atom.)

[11]

[0054] The production method of the compound according to the preceding

[10] , wherein the solvent is a mixed solvent of an aprotic polar solvent and a non-aqueous solvent.

[12]

[0056] The production method of the compound according to the preceding

[11] , wherein the aprotic polar solvent is used in an amount of 1 to 10 times by weight of the non-aqueous solvent.

[13]

[0058] The method for producing the compound as described in the preceding item

[11] or

[12] , wherein dimethyl sulfoxide is used as the aforementioned aprotic polar solvent, and toluene is used as the aforementioned non-aqueous solvent.

[0059] [Effects of Invention]

[0060] The compound of the present application is excellent in solvent solubility, and the hardened product thereof has excellent characteristics of low dielectric properties. Therefore, it is a useful material for encapsulation of electrical and electronic components, circuit substrates, carbon fiber composite materials, and the like. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 A GPC chart showing Synthetic Example 1.

[0062] Figure 2 A GPC chart showing Example 1.

[0063] Figure 3 A GPC chart showing Example 1. 1 H-NMR chart.

[0064] Figure 4 A LC-MS chart showing Example 1.

[0065] Figure 5 A HP-LC chart showing Example 1.

[0066] Figure 6 A GPC chart showing Example 2.

[0067] Figure 7 A HP-LC chart showing Example 2.

[0068] Figure 8 A GPC chart showing Example 3.

[0069] Figure 9 A HP-LC chart showing Example 3.

[0070] Figure 10 A GPC chart showing Example 4.

[0071] Figure 11 A HP-LC chart showing Example 4.

[0072] Figure 12 A GPC chart showing Comparative Synthetic Example 1.

[0073] Figure 13 A GPC chart showing Comparative Synthetic Example 2.

[0074] Figure 14The HP-LC chart of Comparative Synthesis Example 2 is shown. DETAILED DESCRIPTION

[0075] The compound of the present embodiment is a compound represented by the following formula (1), and the ratio (area percentage) of the area (time integral value of signal value) of the compound of formula (1) in which n is 1 to the sum of the areas (time integral value of signal value) of the compounds having a structure represented by formula (1) in a chromatogram obtained by gel permeation chromatography (hereinafter, also referred to as GPC) is not more than 50% in the total amount of the aforementioned compound. In the case where the area percentage of the compound having a structure of formula (1) in which n is 1 is 50% or more, there is a concern that crystallization (i.e., reduction in solvent solubility) occurs when the resin solution containing the aforementioned compound represented by formula (1) is stored.

[0076]

[0077] (In formula (1), each of the plurality of R independently represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. p and r are integers of 0 to 4, and q is an integer of 0 to 3. n is a repetition number, and the average value of n is n ave satisfies 1 ≤ n ave ≤ 20.)

[0078] In the aforementioned formula (1), p and r are usually 0 to 4, preferably 0 to 2, and more preferably 0. q is usually 0 to 3, preferably 0 to 2, and more preferably 0. n ave usually satisfies 1 ≤ n ave ≤ 20, preferably 1.1 ≤ n ave ≤ 20, and more preferably 1.1 ≤ n ave ≤ 10, and particularly preferably 1.1 ≤ n ave ≤ 5. The average value of n ave is calculated from the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (1). The number average molecular weight is preferably 200 or more and not more than 5000, more preferably 300 or more and not more than 3000, and particularly preferably 400 or more and not more than 2000. When the number average molecular weight is not more than 5000, purification by water washing becomes easy, and when it is 200 or more, the possibility that the objective compound is volatilized in the solvent distillation step is small.

[0079] In the aforementioned formula (1), R is a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group, preferably a hydrocarbon group having a carbon number of 1 to 10, more preferably a hydrocarbon group having a carbon number of 1 to 5, and particularly preferably a hydrocarbon group having a carbon number of 1 to 3. When R has a small carbon number, molecular vibration is difficult to occur when exposed to high frequency, and therefore, in the case where the aforementioned description is applied to a hydrocarbon group having a carbon number of 1 to 3, the electrical characteristics are particularly excellent.

[0080] In addition, the GPC measurement of the present embodiment is performed under the following conditions.

[0081] GPC

[0082] GPC: On-line degassing device (DGU-20A3R), binary pipette device (LC-20AD), automatic sampler (SIL-20AHT), differential refractive index detector (RID-20A), column oven (CTO-20A), system controller (CBM-20A) (all manufactured by Shimadzu Corporation)

[0083] Column: Shodex KF-603 x 1, KF-602.5 x 1, KF-602 x 1, KF-601 x 1 (all manufactured by Showa Denko K.K.)

[0084] Guard column: Shodex KF-G 4A (manufactured by Showa Denko K.K.)

[0085] Combined eluate: Tetrahydrofuran

[0086] Flow rate: 1.5 ml / min.

[0087] Column temperature: 40°C

[0088] Detection: RI (differential refractive index detector)

[0089] The compound represented by the aforementioned formula (1) sometimes contains, as a by-product, the compounds represented by the following formulas (2) to (4), and the value (a / b) of the sum (a) of the peak areas of the compounds represented by the following formulas (2) to (4) in the chromatogram obtained by high performance liquid chromatography (HP-LC) with respect to the peak area (b) of the compound of formula (1) in which n is 1 is preferably 0.10 or less, more preferably 0.07 or less. Here, the "peak area" means the area surrounded by the straight line connecting the two tails of the peak and the peak. In practice, it is obtained by the approximate value by the half-value width method or the count number output obtained by integrating the peak value (JIS K0214:2013). The compounds represented by the following formulas (2) to (4) have a polar group in their structures, and the dielectric properties deteriorate as the content of these increases. The lower limit of the value of (a / b) can be 0, but it is preferably 0.01. This is because, if it is 0.01 or more, the adhesion, solvent solubility, and compatibility with compounds having a polar group are improved.

[0090]

[0091] (In formula (2), each of the plurality of R is present independently, and represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. s is an integer of 0 to 4.)

[0092]

[0093] (In formula (3), each of the plurality of R's independently represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. Each of the plurality of A's is independently any one of the following formulae (3-a) to (3-c). s is an integer of 0 to 4, and t is an integer of 0 to 3.)

[0094]

[0095] (In formulae (3-a) to (3-c), * indicates a position bonded to the aromatic ring of the compound of formula (3).)

[0096]

[0097] (In formula (4), each of the plurality of R's independently represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. Each of the plurality of B's is independently formula (4-d) or (4-e) below. D is formula (4-f) below. Each of the plurality of s's is independently an integer of 0 to 4, and t is an integer of 0 to 3. One of the five m's in formula (4) is 1, and the remaining four are 0.)

[0098]

[0099] (In formulae (4-d) to (4-f), * indicates a position bonded to the aromatic ring of the compound of formula (4).)

[0100] It is generally considered that the by-products of the compounds represented by the aforementioned formulae (2) to (4) can be removed by purification, but in the case of the compound represented by the aforementioned formula (1), it is difficult to remove the compounds represented by the aforementioned formulae (2) to (4) by purification methods such as distillation, recrystallization, water washing, and the like. Specifically, since the compound represented by the aforementioned formula (1) has a styrene structure as a functional group, it is highly reactive, and in a purification method requiring overheating such as distillation, undesirable polymerization occurs. Furthermore, it is known that the compound represented by the aforementioned formula (1) is a liquid after distillation of the solvent, and it is difficult to form a crystal structure, and thus it is difficult to recrystallize it with a high yield. Also, in Patent Literature 3, water washing has been performed, but the effect is small.

[0101] Accordingly, in the present embodiment, by adjusting the reaction temperature and the amount of solvent and the mixing ratio of the solvent in the synthesis step of the compound represented by the aforementioned formula (1), the amount of generation of the compounds represented by the aforementioned formulae (2) to (4) is controlled. Details of the synthesis method of the compound represented by the aforementioned formula (1) are described later.

[0102] In addition, in the present embodiment, structural analysis is performed by liquid chromatography mass spectrometry (hereinafter also referred to as LC-MS), and the content of the compounds represented by the aforementioned formulae (2) to (4) is analyzed by high performance liquid chromatography (hereinafter also referred to as HP-LC).

[0103] < LC-MS >

[0104] Apparatus: ultra-high performance liquid chromatography (UHPLC) system (Ultimate 3000), mass spectrometer (Q-Exactive (registered trademark)) (both manufactured by Thermo Fisher Scientific)

[0105] Column: ODS-2 (manufactured by GL Sciences)

[0106] Combined eluate: tetrahydrofuran: water = 3: 1 (no gradient)

[0107] Flow rate: 0.5 ml / min.

[0108] Ionization mode: ESI

[0109] Mass range: m / z = 150-2000

[0110] < HP-LC >

[0111] Apparatus: binary liquid transfer device (LC-20AB), on-line degassing device (DGU-20A3R), automatic sample injector (SIL-20A), column oven (CTO-20A), system controller (CBM-20A), photodiode array detector (SPD-M20A) (all manufactured by Shimadzu Corporation)

[0112] Column: ODS-2 (manufactured by GL Sciences)

[0113] Combined eluate: tetrahydrofuran: water = 3: 1 (no gradient)

[0114] Flow rate: 0.5 ml / min.

[0115] Column temperature: 40°C

[0116] Detection: PDA (photodiode array detector)

[0117] Detector: 274 nm

[0118] The hydroxyl equivalent weight of the compound represented by the aforementioned formula (1) is preferably 100,000 g / eq. or less. When the hydroxyl equivalent weight is 100,000 g / eq. or less, the electrical properties and low heat properties are not impaired, and the adhesion, solvent solubility, and compatibility with compounds having a polar group are improved.

[0119] The compound represented by the aforementioned formula (1) is derived from a compound represented by the following formula (5).

[0120]

[0121] (In formula (5), R which exists plural is independently present, and represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group. p, r are integers of 0 to 4, q is an integer of 0 to 3, n is a repeating number, and the average value n ave 1≤n ave ≤20. X represents a halogen atom.)

[0122] The definition of R in the aforementioned formula (5), p, r, q, and the average value n ave of the aforementioned formula (1) are the same. From the viewpoint of reactivity and stability of the raw material, when R represents a halogenated alkyl group, the halogen atom in R and as X is preferably a bromine atom or a chlorine atom, and particularly preferably a bromine atom.

[0123] The compound represented by the aforementioned formula (1) can be obtained, for example, by a method in which the compound represented by the aforementioned formula (5) is subjected to dehydrohalogenation in the presence of a basic catalyst in a solvent. The amount of the solvent used is preferably 4 to 7 times by weight of the compound represented by formula (5).

[0124] As the solvent used, a non-protic polar solvent is preferable, and examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and the like, and two or more kinds thereof can also be used in combination.

[0125] Further, it is also preferable to use a non-protic polar solvent and a non-aqueous solvent in combination to form a mixed solvent. At this time, as the non-protic polar solvent, dimethyl sulfoxide, dimethyl formamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone are preferable. As the non-aqueous solvent, benzene, toluene, xylene, mesitylene, hexane, cyclohexane, methylcyclohexane are preferable. Among these, the most preferable combination is dimethyl sulfoxide and toluene.

[0126] In the aforementioned mixed solvent, the aforementioned non-protic polar solvent is preferably used at 1 to 10 times by weight of the aforementioned non-aqueous solvent, more preferably 1 to 8 times, and particularly preferably 2 to 6 times. If it is less than 1 times, the reaction is difficult to proceed, and there is a concern that the raw material remains. If it exceeds 10 times, the amount of the compound represented by the aforementioned formula (2) to (4) tends to increase, although the reaction promoting effect is high. This reaction proceeds in a state in which the reaction is separated into two layers of a non-protic polar solvent layer and a non-aqueous solvent layer in the latter half of the reaction, and therefore from the viewpoint of controlling the reactivity at the interface, the above range is preferable.

[0127] The total amount of solvent used is preferably 1 to 9 times by weight, more preferably 2 to 8 times by weight, and particularly preferably 3 to 7 times by weight, relative to the compound represented by the aforementioned formula (5). If the amount is less than 1 times by weight, there is a concern that the stirring will become difficult due to salt precipitation, and if the amount is more than 9 times by weight, there is a concern that the kettle efficiency (the amount of resin that can be synthesized in one batch) will be significantly reduced.

[0128] The reaction temperature is preferably 0 to 80°C, more preferably 10 to 70°C, and even more preferably 26 to 60°C. If the temperature is less than 0°C, there is a concern that the reaction will not proceed sufficiently, and if the temperature is higher than 80°C, there is a concern that the polymerization of the styrene structure will occur concurrently, and the gelation will proceed.

[0129] The catalyst is not particularly limited, but examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. Since the dehydrohalogenation reaction does not proceed completely, a large excess of an aprotic polar solvent relative to the substrate can be used, and the dehydrohalogenation reaction can be performed multiple times, such as 2 or 3 times or more. For example, after washing the solution obtained by subjecting the compound represented by the aforementioned formula (2) to a dehydrohalogenation reaction in the presence of an organic solvent and a basic catalyst, the solution can be returned to the reaction vessel again, and the basic catalyst can be added again to allow the reaction to proceed. In this way, the degree of dehydrohalogenation can be improved. That is, the mass concentration of residual halogen contained in the target compound can be reduced. The mass concentration of residual halogen is preferably 1 to 10,000 ppm in the target product, more preferably 1 to 1,000 ppm, and even more preferably 1 to 750 ppm. If the mass concentration of residual halogen contained in the compound represented by the aforementioned formula (1) is high, molecular vibrations will occur when the compound is exposed to high-frequency waves, and there is a concern that the electrical properties such as the dielectric loss tangent will be adversely affected. In addition, if the mass concentration of residual halogen is high, there is a concern that the risk of problems such as metal corrosion and ion migration will increase in environmental tests such as HAST (High Accelerated Stress Test), and thus the halogen content described above is preferred.

[0130] The method of producing the compound represented by the aforementioned formula (5) is not particularly limited, but for example, a compound having a (2-bromoethyl)benzene structure can be reacted with a bis-halogenated methyl aryl compound (or a bis-hydroxymethyl aryl compound, etc.) in the presence of an acid catalyst such as hydrochloric acid or sulfonic acid, activated clay, etc., or a compound having a (2-bromoethyl)benzene structure can be reacted with a bis-hydroxymethyl aryl compound in the presence of an acid catalyst such as hydrochloric acid or sulfonic acid, activated clay, etc. In the case of using a sulfonic acid or the like as a catalyst, the extraction step can be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene can be used alone, or a non-aromatic hydrocarbon such as cyclohexane or toluene can be used in combination. After extraction, the organic layer is washed with water until the waste water becomes neutral, and the solvent and excess compound having a (2-bromoethyl)benzene structure are distilled off using an evaporator or the like, whereby a compound having at least two or more 2-bromoethylbenzene structures in the molecule of interest can be obtained.

[0131] The charge ratio of the compound having a (2-bromoethyl)benzene structure is preferably 1.0 to 4.0 times, more preferably 1.0 to 3.0 times, and still more preferably 1.0 to 2.0 times, relative to 1 mole of the bis-halogenated methyl aryl compound (or bis-hydroxymethyl aryl compound, etc.). When the charge ratio is 4.0 times or less, significant crystallization can be avoided when the resin solution containing the compound represented by the aforementioned formula (1) is stored in a cold or frozen state. Furthermore, when the charge ratio is 1.0 times or more, significant production of high molecular weight substances can be avoided, and purification by water washing can be performed.

[0132] In the compound represented by the aforementioned formula (5), the content of the compound in which n in formula (5) is 1 can be obtained from the ratio (area percentage) of the area of the slice data of the compound in which n in formula (5) is 1 to the sum of the areas (time integral values of the signal values) of the slice data of the compounds represented by formula (5), using an RI (differential refractive index) detector for GPC analysis. The content of the compound in which n in the aforementioned formula (5) is 1 (area percentage) is preferably 25 to 75%, more preferably 30 to 60%, and still more preferably 35 to 50%. When it is more than 75%, significant crystallization can occur when the resin solution containing the compound represented by the aforementioned formula (1) is stored in a cold or frozen state. Furthermore, when it is less than 25%, there is a concern that the reactivity of high molecular weight substances will decrease. This is because the higher the high molecular weight substances are when the compound represented by the aforementioned formula (1) derived from the compound represented by the aforementioned formula (5) is synthesized under the aforementioned preferred conditions, the more difficult the reaction becomes.

[0133] As the compound having a (2-bromoethyl)benzene structure, for example, (2-bromoethyl)benzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, 1-(2-bromoethyl)-2,6-dimethylbenzene, and the like can be given, but are not limited to these. These can be used alone, or two or more kinds can be used in combination. The larger the carbon number, the more the solvent solubility is improved, but since the heat resistance is lowered, it is preferable that it be unsubstituted or substituted with an alkyl group having a carbon number of 1 to 3, more preferable that it be unsubstituted or substituted with an alkyl group having a carbon number of 1 to 2, and most preferable that it be unsubstituted or substituted with a methyl group.

[0134] As the dihalogenated methyl aryl compound, for example, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-diiodobenzene, m-diiodobenzene, p-diiodobenzene, and the like can be given, but are not limited to these. These can be used alone, or two or more kinds can be used in combination. From the viewpoint of the reactivity of the raw material at the time of synthesis, a chlorine-based compound, a bromine-based compound, an iodine-based compound are preferable, and a chlorine-based compound, a bromine-based compound are more preferable.

[0135] As the dihydroxymethyl aryl compound, for example, o-phenyleneglycol, m-phenyleneglycol, p-phenyleneglycol, and the like can be given, but are not limited to these. These can be used alone, or two or more kinds can be used in combination. The amount of use of these is preferably 0.05 to 0.8 parts by mass, and more preferably 0.1 to 0.6 parts by mass, with respect to 1 part by mass of the compound having a (2-bromoethyl)benzene structure.

[0136] In the reaction of the compound having the (2-bromoethyl)benzene structure with a halogenated methyl aryl compound or the like, a Lewis acid such as aluminum chloride, zinc chloride, activated clay, acid clay, white carbon, zeolite, aluminum silicate, an acidic ion exchange resin, or the like can be used in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid as the catalyst, as needed. These can be used alone or in combination with two or more. The amount of the catalyst used is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, relative to 1 mol of the compound having the (2-bromoethyl)benzene structure used. If the amount of the catalyst used is too large, the viscosity of the reaction solution becomes too high, and stirring becomes difficult. If the amount of the catalyst used is too small, the reaction becomes slow. The reaction can be performed in an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, as needed. For example, in a mixed solution of the compound having the (2-bromoethyl)benzene structure, the halogenated methyl aryl compound, and the solvent, an acidic catalyst is added, and water is removed from the system by azeotropy in the presence of the catalyst containing water. Subsequently, the reaction is performed at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 40 hours. After the reaction is completed, the acidic catalyst can be neutralized with an aqueous base, but the neutralization can be omitted and the water washing step can be directly performed. In the water washing step, a non-water-soluble organic solvent is added to the oil layer, and the water washing is repeated until the waste water becomes neutral.

[0137] The softening point of the compound represented by the aforementioned formula (5) is preferably 80°C or lower, more preferably 70°C or lower. If the softening point is 80°C or lower, the viscosity is low when the compound represented by the aforementioned formula (5) is derived to the compound represented by the aforementioned formula (1). Accordingly, the flowability is easily ensured, the impregnability of the fibrous material such as glass cloth and carbon fiber is not impaired, and the hardening resin composition is easily made into a semi-hardened state (B-stage) such as a prepreg. In the case where a dilution solvent is added to reduce the viscosity, the hardening resin composition can not be sufficiently attached to the fibrous material in the impregnation step.

[0138] [Polymerization inhibitor]

[0139] The compound and the hardening resin composition of the present embodiment can contain a polymerization inhibitor. By containing the polymerization inhibitor, the storage stability is improved, and the reaction start temperature can be controlled. By controlling the reaction start temperature, the flowability is easily ensured, the impregnability of the fibrous material such as glass cloth is not impaired, and the hardening resin composition is easily made into a semi-hardened state (B-stage) such as a prepreg. If the polymerization reaction excessively proceeds at the time of the prepreg, problems such as difficulty in lamination easily occur in the lamination step.

[0140] The polymerization inhibitor can be added before or after the synthesis of the compound represented by the aforementioned formula (1). The amount of the polymerization inhibitor used is 0.008 to 1 parts by weight, preferably 0.01 to 0.5 parts by weight, relative to 100 parts by weight of the compound represented by the aforementioned formula (1).

[0141] As the polymerization inhibitor, for example, phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, nitroxyl radical-based, and the like can be exemplified. In addition, one kind of the polymerization inhibitor can be used, or a plurality of kinds can be used in combination. Among these, in the present embodiment, a polymerization inhibitor of phenol-based, hindered amine-based, nitroso-based, or nitroxyl radical-based is preferred.

[0142] As the above-mentioned phenol-based polymerization inhibitors, monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyl toluene, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl aniline)-1,3,5-triazine, 2,4-bis[(octylthio)methyl] o-cresol, and the like, biphenols such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-bisvinyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphinic acid-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl] 2,4,8,10-tetraoxaspiro[5,5]undecane, calcium bis(3,5-di-tert-butyl-4-hydroxybenzylsulfonate), and the like, high molecular weight phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and the like, but are not limited to these.

[0143] As the above-mentioned sulfur-based polymerization inhibitors, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like, but are not limited to these.

[0144] As the above phosphorus-based polymerization inhibitor, phosphite esters such as triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxy carbonyl) ethyl} phenyl] hydrogen phosphite, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, and the like, but are not limited to these.

[0145] As the above hindered amine-based polymerization inhibitor, Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, Adekastab LA-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb 2020 FDL, Chimassorb 944 FDL, Chimassorb 944 LD, Tinuvin 622 SF, Tinuvin PA 144, Tinuvin 765, Tinuvin 770 DF, Tinuvin XT 55 FB, Tinuvin 111 FDL, Tinuvin 783 FDL, Tinuvin 791 FB, and the like manufactured by ADEKA CORPORATION, but are not limited to these.

[0146] As the above nitroso-based polymerization inhibitor, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxylamine (cupferron), and the like, but are not limited to these. Among these, the ammonium salt of N-nitrosophenylhydroxylamine (cupferron) is preferred.

[0147] As the nitroxyl radical-based polymerization inhibitor described above, for example, di-tert-butyl nitroxyl, 2,2,6,6-tetramethylpiperidine-1-oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-oxyl-2,2,6,6-tetramethylpiperidine-1-oxide, 4-amine-2,2,6,6-tetramethylpiperidine-1-oxide, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxide, and the like can be exemplified, but are not limited to these.

[0148] [Polyphenylene ether compound]

[0149] The curable resin composition of the present embodiment can contain a polyphenylene ether compound.

[0150] As the polyphenylene ether compound, from the viewpoint of heat resistance and electrical properties, a polyphenylene ether compound having an ethylenically unsaturated bond is preferable, and a polyphenylene ether compound having an acryl group, a methacryl group, or a styrene structure is more preferable. As commercially available products, SA-9000 (manufactured by SABIC, polyphenylene ether compound having a methacryl group) and OPE-2St1200 (manufactured by Mitsubishi Gas Chemical, polyphenylene ether compound having a styrene structure), and the like can be exemplified.

[0151] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and still more preferably 2000 to 4000. When the molecular weight is less than 500, there is a tendency that the heat resistance of the cured product is insufficient. In addition, when the molecular weight is more than 5000, the melt viscosity becomes high, and sufficient flowability cannot be obtained, and there is a tendency that the molding failure becomes easy. In addition, the reactivity is also reduced, the curing reaction needs to be performed for a long time, the unreacted material not incorporated into the curing system increases, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product decreases.

[0152] When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, excellent dielectric properties are maintained, and excellent heat resistance, moldability, and the like can be exhibited. In addition, the number average molecular weight here can be measured using, for example, gel permeation chromatography.

[0153] The polyphenylene ether compound can be obtained by polymerization, or can be obtained by redistribution reaction of a high-molecular-weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. Furthermore, radical polymerizability can be imparted by reacting these as raw materials with a compound having an ethylenic unsaturated bond such as methacryloyl chloride, acryloyl chloride, chloromethylstyrene, and the like. The polyphenylene ether compound obtained by redistribution reaction is obtained, for example, by heating a high-molecular-weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator and performing redistribution reaction. The polyphenylene ether compound obtained by such redistribution reaction is preferable because, due to the hydroxyl groups derived from the phenolic compound imparting hardness present at both ends of the molecular chain, not only can the high heat resistance be further maintained, but even after modification with a compound having an ethylenic unsaturated bond, a functional group can be introduced at both ends of the molecular chain, and thus is preferable. Furthermore, the polyphenylene ether compound obtained by polymerization exhibits excellent flowability, and thus is preferable.

[0154] Adjustment of the molecular weight of the polyphenylene ether compound can be performed by adjusting the polymerization conditions and the like in the case of a polyphenylene ether compound obtained by polymerization. Furthermore, in the case of a polyphenylene ether compound obtained by redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction and the like. More specifically, the amount of the phenolic compound used in the redistribution reaction and the like can be considered for adjustment. That is, the more the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, as the high-molecular-weight polyphenylene ether compound subjected to the redistribution reaction, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used. Furthermore, the phenolic compound used in the aforementioned redistribution reaction is not particularly limited, but a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule such as bisphenol A, phenol novolac, cresol novolac, and the like is preferably used. These can be used alone, or two or more can be used in combination.

[0155] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1,000 parts by mass, more preferably 10 to 750 parts by mass, with respect to 100 parts by mass of the compound represented by the aforementioned formula (1). The content of the polyphenylene ether compound is within the above range, and thus not only is the heat resistance and the like excellent, but a cured product in which the excellent dielectric properties possessed by the polyphenylene ether compound are sufficiently exhibited can be obtained, and thus is preferable.

[0156] [Polybutadiene and modified products thereof]

[0157] The curable resin composition of the present embodiment can contain polybutadiene and modified products thereof.

[0158] The polybutadiene and modified product thereof means a compound having a polybutadiene structure or a structure derived from a polybutadiene in the molecule. The structure derived from a polybutadiene can be changed to a single bond by hydrogen addition of a part of unsaturated bonds or all.

[0159] As the polybutadiene and modified product thereof, for example, polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth)acrylate polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene butadiene rubber, and the like can be exemplified, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination. Among these, from the viewpoint of dielectric properties, polybutadiene or styrene butadiene rubber is preferable. As the styrene butadiene rubber (SBR), for example, RICON-100, RICON-181, RICON-184 (all of which are manufactured by CRAY VALLEY), 1,2-SBS (manufactured by JSR), and the like can be exemplified, and as the polybutadiene, B-1000, B-2000, B-3000 (all of which are manufactured by JSR), and the like can be exemplified. As the molecular weight of the polybutadiene and styrene butadiene rubber, the weight average molecular weight is preferably 500 to 10,000, more preferably 750 to 7,500, and still more preferably 1,000 to 5,000. Below the lower limit of the above range, the volatile amount is large, and it is difficult to adjust the solid content at the time of production of a prepreg, and above the upper limit of the above range, the compatibility with other curable resins deteriorates. In general, in the case of a compound containing a heteroatom such as oxygen or nitrogen such as a bis-maleimide or a poly-maleimide, the compatibility with a compound mainly composed of a hydrocarbon or a compound composed only of a hydrocarbon is difficult to be ensured due to the polarity thereof. On the other hand, the compound represented by the aforementioned formula (1) is excellent in the compatibility with a material having low polarity and low dielectric properties or a compound composed only of a hydrocarbon due to the skeleton design thereof which does not actively introduce a heteroatom such as oxygen or nitrogen.

[0160] The content of the polybutadiene and modified product thereof is not particularly limited, but is preferably 5 to 1,000 parts by mass, and more preferably 10 to 750 parts by mass, with respect to 100 parts by mass of the compound represented by the aforementioned formula (1). The polybutadiene and modified product thereof are preferably within the above range, and not only are excellent in heat resistance and the like, but also a cured product in which the excellent dielectric properties of the polybutadiene and modified product thereof are sufficiently exerted can be obtained, and thus are preferable.

[0161] [Polystyrene and modified product thereof]

[0162] The curable resin composition of the present embodiment can contain a polystyrene and modified product thereof.

[0163] The polystyrene and modified product thereof means a compound having a polystyrene structure or a structure derived from a polystyrene in the molecule.

[0164] As the polystyrene and its modified products, for example, polystyrene, a copolymer of styrene and 2-isopropenyl-2-oxazoline (Epocros RPS-1005, RP-61, both manufactured by NIPPON SHOKUBAI CO., LTD.), SEP (a copolymer of styrene-ethylene and propylene: SEPTON 1020 manufactured by KURARAY CO., LTD.), SEPS (a copolymer of styrene-ethylene and propylene-styrene: SEPTON 2002, SEPTON 2004F, SEPTON 2005, SEPTON 2006, SEPTON 2063, SEPTON 2104, all manufactured by KURARAY CO., LTD.), SEEPS (a block copolymer of styrene-ethylene / ethylene and propylene-styrene: SEPTON 4003, SEPTON 4044, SEPTON 4055, SEPTON 4077, SEPTON 4099, all manufactured by KURARAY CO., LTD.), SEBS (a block copolymer of styrene-ethylene and butylene-styrene: SEPTON 8004, SEPTON 8006, SEPTON 8007L, all manufactured by KURARAY CO., LTD.), SEEPS-OH (a compound having a hydroxyl group at the terminal of a block copolymer of styrene-ethylene / ethylene and propylene-styrene: SEPTON HG252 manufactured by KURARAY CO., LTD.), SIS (a block copolymer of styrene-isoprene-styrene: SEPTON 5125, SEPTON 5127, both manufactured by KURARAY CO., LTD.), hydrogenated SIS (a hydrogenated block copolymer of styrene-isoprene-styrene: HYABRAR 7125F, HYABRAR 7311F, both manufactured by KURARAY CO., LTD.), SIBS (a block copolymer of styrene-isobutylene-styrene: SIBSTAR 073T, SIBSTAR 102T, SIBSTAR 103T, all manufactured by Kaneka Corporation), SEPTON V9827 (manufactured by KURARAY CO., LTD.), and the like can be mentioned, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination. The polystyrene and its modified products are preferably free from an unsaturated bond, and thus have high heat resistance and are difficult to be oxidatively deteriorated. In addition, the weight average molecular weight of the polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with a low molecular weight component having a weight average molecular weight of 50 to 1,000 or so and an oligomer component having a weight average molecular weight of 1,000 to 5,000 or so deteriorates in addition to the polystyrene compound, and it is difficult to ensure the mixing and solvent stability, and thus it is preferably 10,000 to 300,000 or so.

[0165] The content of polystyrene and its modified product is not particularly limited, but is preferably 5 to 1000 parts by mass, more preferably 10 to 750 parts by mass, relative to 100 parts by mass of the compound represented by the aforementioned formula (1). When the polystyrene and its modified product falls within the above range, not only is the heat resistance and the like excellent, but also a hardened product in which the excellent dielectric properties of the polystyrene and its modified product are sufficiently exhibited can be obtained, and thus the polystyrene and its modified product is preferred.

[0166] [Inorganic Filler]

[0167] The curable resin composition of the present embodiment can also contain an inorganic filler. As the inorganic filler, for example, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, block talc, spinel, mullite, titanium dioxide, talc, clay, iron oxide asbestos, glass powder, or inorganic fillers in which these are made spherical or are pulverized, and the like can be exemplified, but are not limited thereto. Furthermore, one kind can be used, or a plurality of kinds can be used in combination.

[0168] In the case of obtaining a curable resin composition for sealing a semiconductor, the amount of the inorganic filler used is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, relative to 100 parts by mass of the curable resin composition. Furthermore, in the case of obtaining a curable resin composition for a substrate material such as an interlayer insulating layer-forming material, a copper laminate sheet, and a prepreg, an RCC, and the like, the amount of the aforementioned inorganic filler used is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the curable resin composition.

[0169] [Hardening Accelerator]

[0170] The curable resin composition of the present embodiment can improve the curability by adding a hardening accelerator. As the hardening accelerator, an anion-based hardening accelerator that generates anions by irradiation of ultraviolet rays or visible light or heating to accelerate the hardening reaction, or a cation-based hardening accelerator that generates cations by irradiation of ultraviolet rays or visible light or heating to accelerate the hardening reaction is preferred.

[0171] As the anion-based hardening accelerator, imidazoles such as 2-methylimidazole, 2- ethylimidazole, 2-ethyl-4-methylimidazole, and the like, trialkyl amines such as triethylamine, tributylamine, and the like, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6- tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like can be exemplified, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable. In addition to these, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, hexadecyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide, and the like can be exemplified.

[0172] As the cation-based hardening accelerator, quaternary phosphonium salts (the counter ion of the quaternary salt is halogen, an organic acid ion, a hydroxide ion, and the like, and is not particularly specified, but an organic acid ion and a hydroxide ion are particularly preferable) such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt, and the like, tin octoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), zinc phosphate esters (zinc octylphosphate, zinc stearylphosphate), and the like can be exemplified, but are not limited thereto. In addition, one type can be used, or a plurality of types can be used in combination.

[0173] The blending amount of the hardening accelerator is preferably 0.01 to 5.0 parts by mass, and more preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of the total of the nonvolatile components other than the inorganic filler (filler) in the hardenable resin composition.

[0174] [Polymerization Initiator]

[0175] The hardenable resin composition of the present embodiment can also be improved in hardenability by the addition of a polymerization initiator. The polymerization initiator is a compound that enables the polymerization of an olefin functional group such as an ethylenic unsaturated bond, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Among these, a radical polymerization initiator having hardenability and moderate stability is preferably used. In the case of an olefin metathesis polymerization initiator such as a Schrock catalyst having molybdenum as the central metal, an anionic polymerization initiator such as BuLi, and a cationic polymerization initiator such as triethylaluminum, the stability is poor due to reactions with moisture in the air and the like.

[0176] The radical polymerization initiator means a compound that enables the start of a chain polymerization reaction by the generation of radicals through the irradiation of ultraviolet rays or visible light or heating. As the radical polymerization initiator that can be used, organic peroxides, azo-based compounds, benzopinacol, and the like can be exemplified, and organic peroxides are preferably used in terms of hardening temperature control and the inhibition of outgassing, and the influence on the electrical characteristics of the decomposition products is small.

[0177] As the above-mentioned organic peroxide, there can be mentioned, for example, ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, and the like; diacyl peroxides such as benzoyl peroxide and the like; dialkyl peroxides such as dicumyl peroxide, 1,3-bis-(tert-butylperoxyisopropyl)-benzene, and the like; alkyl peresters such as tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy cyclohexane, and the like; peroxyketals such as α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneopentanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-amyl peroxybenzoate, and the like; peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, 1,6-bis(tert-butylperoxycarbonyloxy)hexane, and the like; hydroperoxides such as tert-butyl hydroperoxide, cumyl hydroperoxide, tert-butyl peroxyoctoate, lauryl peroxide, and the like, but not limited to these. One kind can be used, or a plurality of kinds can be used in combination. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxydicarbonates are preferred, and dialkyl peroxides are more preferred.

[0178] As the above-mentioned azo compound, there can be mentioned, for example, azobis isobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like, but not limited to these. One kind can be used, or a plurality of kinds can be used in combination.

[0179] As the amount of the polymerization initiator to be added, it is preferred that, in the case where the total of the non-volatile components other than the inorganic filler (filler) in the curable resin composition is taken as 100 parts by mass, the amount of the polymerization initiator is 0.01 to 5 parts by mass, and it is particularly preferred that the amount is 0.01 to 3 parts by mass. If the amount of the polymerization initiator used is less than 0.01 parts by mass, there is a concern that the molecular weight cannot be sufficiently elongated at the time of polymerization, and if the amount is more than 5 parts by mass, there is a concern that the dielectric properties such as the dielectric constant, the dielectric loss tangent, and the like are impaired.

[0180] [Flame Retardant]

[0181] The curable resin composition of the present embodiment can use a flame retardant. As the flame retardant, there can be mentioned, for example, halogen-based flame retardants, inorganic-based flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, and the like), phosphorus-based flame retardants, and the like, but from the viewpoint of achieving halogen-free flame retardancy, a phosphorus-based flame retardant is preferred.

[0182] As the above-mentioned phosphorus-based flame retardant, a reactive phosphorus-based flame retardant or an additive phosphorus-based flame retardant can be used. As specific examples, phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-di-2, 6-xylenyl phosphate, 1, 3-phenylene bis (dixylenyl phosphate), 1, 4-phenylene bis (dixylenyl phosphate), 4, 4'-diphenyl (dixylenyl phosphate), phosphoranes such as 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10 (2, 5-dihydroxyphenyl) -10H-9-oxo-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with active hydrogen of the above-mentioned phosphoranes, red phosphorus, and the like can be used, but are not limited to these. One kind can be used, or a plurality of kinds can be used in combination. Among the above-mentioned examples, phosphoric acid esters, phosphoranes, or phosphorus-containing epoxy compounds are preferred, and 1, 3-phenylene bis (dixylenyl phosphate), 1, 4-phenylene bis (dixylenyl phosphate), 4, 4'-diphenyl (dixylenyl phosphate), or a phosphorus-containing epoxy compound is particularly preferred.

[0183] When the total of non-volatile components other than the inorganic filler (filler) in the hardening resin composition is taken as 100 parts by mass, the content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass. If it is less than 0.1 parts by mass, there is a concern that the flame retardancy becomes insufficient, and if it is more than 0.6 parts by mass, there is a concern that the moisture absorption of the hardened product and the dielectric properties are adversely affected.

[0184] [Light stabilizer]

[0185] The curable resin composition of the present embodiment can use a light stabilizer. As the light stabilizer, a light stabilizer of a hindered amine system is preferable, and a HALS (Hindered Amine Light Stabilizers) or the like is particularly preferable. As the HALS, for example, the following can be listed: a reaction product of dibutylamine with 1,3,5-triazine and N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a reaction product of succinic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly{[6-(1,1,3,3-tetramethylbutyl)aminyl-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)iminyl}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)iminyl]}, bis(1,2,2,6,6-pentamethyl-4-piperidyl)〔〔3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl〕methyl〕butyric acid, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacic acid ester, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid ester, and the like, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0186] The content of the light stabilizer is preferably in the range of 0.001 to 10 parts by mass, with the total of non-volatile components other than the inorganic filler (filler) in the curable resin composition being taken as 100 parts by mass. If it is less than 0.001 parts by mass, the light stabilizing effect can not be sufficiently exhibited, and if it is more than 10 parts by mass, the moisture absorption and dielectric properties of the hardened product can be adversely affected.

[0187] [Binder resin]

[0188] The curable resin composition of the present embodiment can use a binder resin. As the binder resin, for example, the following can be listed: a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a silicone resin, and the like, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0189] The amount of the binder resin is preferably in the range of 0.05 to 50 parts by mass, and more preferably in the range of 0.05 to 20 parts by mass, with the total of non-volatile components other than the inorganic filler (filler) in the curable resin composition being taken as 100 parts by mass, without impairing the flame retardancy and heat resistance of the hardened product.

[0190] [additives]

[0191] The curable resin composition of the present embodiment can use an additive. As the additive, for example, a coloring agent such as a modified acrylonitrile copolymer, polyethylene, a fluororesin, a silicone gel, a silicone oil, a surface treatment agent for a filler of a silane coupling agent, a releasing agent, carbon black, phthalocyanine blue, phthalocyanine green, and the like can be exemplified.

[0192] The blending amount of the additive is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, with respect to 100 parts by mass of the curable resin composition.

[0193] The curable resin composition of the present embodiment can further use an epoxy resin, an active ester compound, a phenol resin, an amine resin, a maleimide compound, a compound having an ethylenic unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, a cyanate ester resin, and the like, and one kind thereof can be used, or a plurality of kinds thereof can be used in combination. Among these compounds, in terms of the balance of heat resistance, adhesion, and dielectric properties, it is preferable to contain a compound having an ethylenic unsaturated bond and a cyanate ester resin. By containing these compounds, the brittleness of the cured product can be improved, and the adhesion to a metal can be improved, and the cracking of a package can be suppressed in a reliability test such as reflow soldering and a cold-heat cycle.

[0194] Unless otherwise specified, the use amount of the aforementioned compound is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, with respect to the compound represented by the aforementioned formula (1). In addition, the lower limit value is preferably 0.1 times by mass or more, more preferably 0.25 times by mass or more, and particularly preferably 0.5 times by mass or more. By being within the aforementioned range, the effects of each of the compounds to be added can be added while the effects of the heat resistance and the dielectric properties of the compound represented by the aforementioned formula (1) are utilized. With respect to these components, the following exemplified components can be used.

[0195] [epoxy resins]

[0196] As the epoxy resin, the following preferred epoxy resins are exemplified, but are not limited to these. In addition, the epoxy resin can be in a liquid state or a solid state, and one kind thereof or a plurality of kinds thereof can be used in combination.

[0197] As the liquid epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure, etc. can be exemplified. As specific examples, "RE310S", "RE410S" (both manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corp., naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corp., bisphenol A type epoxy resin), "jE807", "1750" (all manufactured by Mitsubishi Chemical Corp., bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corp., phenol novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corp., glycidyl amine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase Chemtex Corp., glycidyl ester type epoxy resin), "CELLOXIDE 2021P" (manufactured by DAICEL Corp., alicyclic epoxy resin having an ester skeleton), "PB-3600" (manufactured by DAICEL Corp., epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. can be exemplified. These can be used singly or in combination of two or more.

[0198] As the solid epoxy resin, for example, a resorcinol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type 4-functional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a pyrogallol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthalene ether type epoxy resin, an onion type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a tetraphenyl ethane type epoxy resin, preferably a naphthol type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin can be exemplified. As specific examples, "HP4032H" (manufactured by DIC Corporation, naphthalene type epoxy resin), "HP-4700", "HP-4710" (both of which are manufactured by DIC Corporation, naphthalene type 4-functional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (all of which are manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all of which are manufactured by DIC Corporation, naphthalene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., pyrogallol type epoxy resin), "NC-7000L", "NC-7300" (both of which are manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all of which are manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H" (all of which are manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all of which are manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, resorcinol type epoxy resin), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, onion type epoxy resin), "PG-100", "CG-500" (both of which are manufactured by Osaka Gas Chemicals Co., Ltd., fluorene type epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenyl ethane type epoxy resin), and the like can be exemplified.These can be used alone 1 or can be used in combination of 2 or more.

[0199] [Active ester compound]

[0200] The active ester compound means a compound having at least one ester bond in the structure, and having an aliphatic chain, an aliphatic ring, or an aromatic ring bonded on both sides of the ester bond. As the active ester compound, a compound having 2 or more highly reactive ester groups in 1 molecule, such as phenol esters, thiol phenol esters, N-hydroxy amine esters, esters of heterocyclic hydroxyl compounds, and the like, which is obtained by condensation reaction of at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound, with at least one compound of a hydroxyl compound or a thiol compound. In particular, from the viewpoint of heat resistance improvement, it is preferable to be obtained from a carboxylic acid compound or an acid chloride and a hydroxyl compound, and as the hydroxyl compound, a phenol compound or a naphthol compound is preferable. The active ester compound can be used alone 1 or can be used in combination of 2 or more.

[0201] As the above carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like can be exemplified.

[0202] As the above acid chloride, for example, acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl dichloride, succinyl dichloride, diglycolic acid dichloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecanedioic acid dichloride, nonanoyl chloride, 2,5-furandicarboxylic acid dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, benzene tricarboxylic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azobenzene dicarboxylic acid dichloride, and the like can be exemplified.

[0203] As the above phenol compound and the above naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-dihydroxybenzene, a-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, m-trihydroxyphenol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, and the like can be exemplified. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensation of 1 molecule of dicyclopentadiene and 2 molecules of phenol.

[0204] As preferable specific examples of the active ester compound, there can be mentioned: an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, an active ester compound containing a benzoylated product of phenol novolak, a compound described in International Publication No. 2020 / 095829, Example 2, a compound disclosed in International Publication No. 2020 / 059625, and the like. Among them, more preferable are the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure. The dicyclopentadiene type diphenol structure means a 2-valent structural unit composed of phenylene-dicyclopentene-phenylene.

[0205] As commercially available products of the active ester compound, for example, as the active ester compound containing a dicyclopentadiene type diphenol structure, there can be mentioned "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation), as the active ester compound containing a naphthalene structure, there can be mentioned "EXB9416-70BK" (manufactured by DIC Corporation), as the active ester compound containing an acetylated product of phenol novolak, there can be mentioned "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound containing a benzoylated product of phenol novolak, there can be mentioned "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), as the active ester-based hardener belonging to the acetylated product of phenol novolak, there can be mentioned "DC808" (manufactured by Mitsubishi Chemical Corporation), and as the active ester-based hardener containing a phosphorus atom, there can be mentioned "EXB-9050L-62M" (manufactured by DIC Corporation), and the like.

[0206] As for the blending ratio of the active ester compound and the epoxy resin, the ratio (a / β) of the active ester equivalent (a) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and still more preferably 0.90 to 1.10. In the case of outside the above range, there is a concern that too many epoxy groups or active ester groups remain in the system, and there is a concern that characteristics deteriorate in high-temperature storage tests (150°C, 1000 hours, etc.) and long-term reliability tests under high-temperature high-humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[0207] [Phenol resin]

[0208] The phenol resin means a compound having 2 or more phenolic hydroxyl groups in the molecule. As the phenol resin, for example, a reactant of phenol and aldehyde, a reactant of phenol and diene compound, a reactant of phenol and ketone, a reactant of phenol and substituted biphenyl, a reactant of phenol and substituted phenyl, a reactant of bisphenol and aldehyde, and the like can be exemplified, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0209] The following exemplifies specific examples of the above-mentioned raw materials, but is not limited to these.

[0210] <Phenol>

[0211] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, and the like.

[0212] <Aldehyde>

[0213] Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like.

[0214] <Diene compound>

[0215] Dicyclopentadiene, terpene, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindenene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like.

[0216] <Ketone>

[0217] Acetone, methyl ethyl ketone, methyl isobutyl ketone, phenylacetone, benzophenone, fluorenone, and the like.

[0218] <Substituted biphenyl>

[0219] 4,4'-Bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, and the like.

[0220] <Substituted phenyl>

[0221] 1,4-Bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, and the like.

[0222] [Amine resin]

[0223] The amine resin means a compound having two or more amine groups in a molecule. As the amine resin, for example, diamino diphenyl methane, diamino diphenyl sulfone, isophorone diamine, naphthalene diamine, aniline novolak (a reaction product of aniline and formalin), N-methylaniline novolak (a reaction product of N-methylaniline and formalin), o-ethylaniline novolak (a reaction product of o-ethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, aniline resin obtained by reacting aniline and xylene chloride, a reaction product of aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bis aniline, 4,4'-(1,4-phenylenediisopropylidene)bis aniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, and the like, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0224] [Maleimide compound]

[0225] The maleimide compound means a compound having one or more maleimide groups in the molecule. The curable resin composition of the present embodiment can contain a maleimide compound. As the maleimide compound, for example, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene, Xyloc type maleimide compound (ANILIX maleimide, manufactured by Mitsui Chemicals, Inc.), biphenyl aralkyl type maleimide compound (a compound solidified by solvent distillation under reduced pressure of a resin solution containing a maleimide compound (M2) described in Example 4 of Japanese Patent Application Publication No. 2009-001783), bisaminophenylphenyl type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compound having an indane structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, maleimide compounds disclosed in "Material Stage Vol. 18, No. 12 2019 "Continued. Epoxy Resin CAS Number Story ~ Hardener CAS Number Memorandum 31st Round Bismaleimide (1)", and "Material Stage Vol. 19, No. 2 2019 "Continued. Epoxy Resin CAS Number Story ~ Hardener CAS Number Memorandum 32nd Round Bismaleimide (2)", and the like, but not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0226] The addition amount of the maleimide compound with respect to the compound represented by the aforementioned formula (1) is preferably in the range of 10 mass or less, more preferably 5 mass or less, and particularly preferably 3 mass or less. In addition, the lower limit is preferably 0.01 mass or more, and more preferably 0.1 mass or more. By being in the above range, the effects of heat resistance, dielectric properties, and low water absorption of the compound represented by the aforementioned formula (1) can be exerted.

[0227] [Compound containing ethylenic unsaturated bond]

[0228] The compound containing an ethylenic unsaturated bond means a compound having one or more ethylenic unsaturated bonds which can be polymerized by heat or light in the molecule, with or without using a polymerization initiator.

[0229] As the compound containing an ethylenic unsaturated bond, for example, the following can be listed: a reactant of the aforementioned phenol resin and a halogen-based compound containing an ethylenic unsaturated bond (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, methacryloyl chloride, etc.), a reactant of a phenol containing an ethylenic unsaturated bond (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and a halogen-based compound (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), a reactant of an epoxy resin or an alcohol and a (meth)acrylic acid (acrylic acid, methacrylic acid, etc.), and acid-modified products of these, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0230] [Isocyanate resin]

[0231] The isocyanate resin means a compound having two or more isocyanate groups in the molecule. As the isocyanate resin, for example, the following can be listed: aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc., aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, etc., polyisocyanates such as a biuret of one kind or more of isocyanate monomers, or an isocyanate body obtained by trimerizing the above diisocyanate compounds, etc., polyisocyanates obtained by urethane reaction of the above isocyanate compounds with a polyol compound, etc., but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0232] [Polyamide resin]

[0233] As the polyamide resin, for example, the following can be listed: a reactant of one kind or more of a diamine, a diisocyanate, an oxazoline, a dicarboxylic acid, a reactant of a diamine and an acid chloride, an open ring polymer of a lactam compound. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0234] The following illustrates specific examples of the above raw materials, but are not limited to these.

[0235] <Diamine>

[0236] Ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, tetradecamethylene diamine, pentadecamethylene diamine, hexadecamethylene diamine, heptadecamethylene diamine, octadecamethylene diamine, nonadecamethylene diamine, eicosamethylene diamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dipodal diamine, cyclohexane diamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylene diamine, norbornane diamine, isophorone diamine, bisaminomethyl tricyclodecane, phenylene diamine, diethyl toluene diamine, naphthalene diamine, diaminodiphenyl methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-toluidine, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)benzidine, 4,4'-(1,4-phenylenediisopropylidene)benzidine, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like.

[0237] <Diisocyanate>

[0238] Phenylene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like.

[0239] <Diacid>

[0240] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium isophthalic acid sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxy diphenyl ether, 4,4'-dicarboxy diphenyl sulfide, and the like.

[0241] <Acid halides>

[0242] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycoloyl chloride, glutaroyl dichloride, suberoyl dichloride, sebacoyl dichloride, adipoyl dichloride, dodecanoyl chloride, nonanoyl chloride, 2,5-furandicarboxylic dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, benzene tricarboxylic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azobenzoyl dichloride, and the like.

[0243] <Lactams>

[0244] ε-caprolactam, ω-undecanolactam, ω-lauryl lactam, and the like.

[0245] [Polyimide resins]

[0246] As the polyimide resin, for example, a reaction product of the aforementioned diamine and the following exemplified tetracarboxylic dianhydride can be exemplified, but is not limited to these. Further, one kind can be used, or a plurality of kinds can be used in combination.

[0247] <Tetracarboxylic dianhydrides>

[0248] 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-chavicine tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxetanyltetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and the like.

[0249] [cyanoate resin]

[0250] The cyanoate resin is a cyanoate compound obtained by reacting a phenol resin with a cyanogen halide, and as specific examples, dicyanate phenyl, tricyanate phenyl, dicyanate naphthalene, dicyanate biphenyl, 2,2'-bis(4-cyanate phenyl)propane, bis(4-cyanate phenyl)methane, bis(3,5-dimethyl-4-cyanate phenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanate phenyl)propane, 2,2'-bis(4-cyanate phenyl)ethane, 2,2'-bis(4-cyanate phenyl)hexafluoropropane, bis(4-cyanate phenyl)sulfone, bis(4-cyanate phenyl)sulfide, phenol novolac cyanoate, a phenol-dicyclopentadiene co-condensate in which a hydroxyl group is converted to a cyanoate group, and the like, but are not limited to these. In addition, one kind can be used, or a plurality of kinds can be used in combination.

[0251] In addition, the synthetic method is described in the cyanoate compound of Japanese Patent Application Publication No. 2005-264154, and since the moisture absorption is low, the flame retardancy is excellent, and the dielectric properties are excellent, it is particularly preferable as the cyanoate compound.

[0252] In order to respond to the need to trimerize the cyanoate group to form a s-triazine ring, a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, and the like can be contained in the cyanoate resin.

[0253] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, with respect to 100 parts by mass of the cyanoate resin.

[0254] The curable resin composition of the present embodiment is obtained by mixing the above components in a predetermined ratio, and is prepared to harden for 30 to 500 seconds at 130 to 180°C, and is sufficiently hardened by post-hardening for 2 to 15 hours at 150 to 200°C, thereby obtaining the hardened product of the present embodiment. In addition, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and after removing the solvent, the curable resin composition is hardened.

[0255] The mixing method of the curable resin composition of the present embodiment is not particularly limited, but the components can be uniformly mixed, and can be prepolymerized. For example, a mixture of the compound represented by the above formula (1) and other compounds is heated in the presence or absence of a hardening accelerator or a polymerization initiator, and in the presence or absence of a solvent, thereby prepolymerizing. Similarly, an amine compound, a compound having an ethylenic unsaturated bond, a maleimide compound, a cyanate compound, a polybutadiene and a modified product thereof, a polystyrene and a modified product thereof, and the like, an inorganic filler, and other additives can be added and prepolymerized. The mixing or prepolymerization of the components is performed in the absence of a solvent, for example, using an extruder, a kneader, a roll mill, or the like, or in the presence of a solvent, using a reactor with a stirring device, or the like.

[0256] As a method of uniformly mixing, the obtained resin composition is kneaded at a temperature in the range of 50 to 100°C using a kneader, a roll mill, a planetary mixer, or the like, thereby obtaining a uniform resin composition. The obtained resin composition can be crushed and molded into a cylindrical ingot shape using a molding machine such as a tablet press, or can be made into a granular powder, or can be made into a powder-shaped molded body, or the obtained composition can be melted on a surface support and molded into a sheet shape having a thickness of 0.05 to 10 mm, thereby obtaining a curable resin composition molded body. The obtained molded body becomes a non-sticky molded body at 0 to 20°C, and even if it is stored at -25 to 0°C for 1 week or more, the flowability and curability are hardly reduced.

[0257] The obtained molded body can be molded into a hardened product using a transfer molding machine or a compression molding machine.

[0258] The curable resin composition of the present embodiment can also be added with an organic solvent to produce a varnish-like composition (hereinafter referred to as a varnish). As needed, the curable resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like to produce a varnish, which is impregnated in a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, or the like and dried by heating, and a prepreg obtained thereby is hot-pressed to produce a cured product of the curable resin composition of the present embodiment. In this case, the amount of the solvent used in the mixture of the curable resin composition of the present embodiment and the solvent is preferably 10 to 70% by weight, more preferably 15 to 70% by weight. In addition, if the composition is liquid, a curable resin cured product containing carbon fiber can be obtained directly by, for example, the RTM method.

[0259] In addition, the curable resin composition of the present embodiment can also be used as a modifier for a film-type composition. Specifically, it can be used in cases where flexibility or the like is to be improved in the B-stage. A film-type resin composition of this kind is obtained by applying the curable resin composition of the present embodiment as a varnish of the aforementioned curable resin composition to a release film, removing the solvent by heating, and then performing B-staging to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0260] The curable resin composition of the present embodiment can also be obtained by heating and melting, lowering the viscosity, and impregnating it in a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or the like to obtain a prepreg. As specific examples, there can be mentioned, for example, glass fiber such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, fiber of an inorganic substance other than glass, and organic fiber such as poly-p-phenyleneterephthalamide (Kevlar (registered trademark), manufactured by DuPont-Toray Co., Ltd.), wholly aromatic polyamide, polyester, poly-p-phenylene benzoxazole, polyimide, and carbon fiber, but the present embodiment is not limited to these. The shape of the substrate is not particularly limited, but there can be mentioned, for example, woven cloth, nonwoven cloth, roving, chopped strand mat, and the like. In addition, as weaving methods for woven cloth, there are known plain weave, basket weave, twill weave, and the like, and the appropriate one can be selected from among these well-known methods in accordance with the intended use and properties. In addition, it is preferable to use woven cloth that has been subjected to a fiber opening treatment or glass cloth that has been subjected to a surface treatment with a silane coupling agent or the like. The thickness of the substrate is not particularly limited, but it is preferably about 0.01 to 0.4 mm. In addition, a prepreg can also be obtained by impregnating a reinforcing fiber in the aforementioned varnish and drying it by heating.

[0261] Further, the prepreg described above can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and can have any other layer. As a method for manufacturing the laminate, there is no particular limitation, and a generally known method can be appropriately used. For example, when a metal-clad laminate is molded, a multistage press, a multistage vacuum press, a continuous molding machine, a high-pressure tank molding machine, or the like can be used, and the laminate can be obtained by stacking the prepregs described above on each other and molding by heating and pressing. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, and more preferably 120 to 270°C. Further, the pressure is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate and the quality is unstable, and if the pressure is too low, bubbles occur and the adhesion between the layers is poor, and therefore, the pressure is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of the present embodiment can preferably be used as a metal-clad laminate described later by having a layer composed of a metal foil.

[0262] The prepreg described above is cut into a desired shape, stacked with a copper foil or the like as needed, and then, by applying pressure to the stack by a press molding method or a high-pressure tank molding method, a sheet winding molding method, or the like, and simultaneously heating and hardening the hardenable resin composition, an electrical / electronic laminate (printed wiring board), a carbon fiber reinforced material can be obtained.

[0263] The hardenable resin composition of the present embodiment can also be used as a resin sheet. As a method for obtaining a resin sheet from the hardenable resin composition of the present embodiment, a method in which the hardenable resin composition is applied to a support film (support) and then dried to form a resin composition layer on the support film can be exemplified. In the case where the hardenable resin composition of the present embodiment is used for a resin sheet, the film is softened under the temperature conditions (70°C to 140°C) of the lamination in a vacuum lamination method, and it is important to exhibit flowability (resin flow) that allows the resin to fill the through holes or vias present in the circuit board at the time of lamination with the circuit board, and the aforementioned components are preferably adjusted to exhibit such characteristics. In addition, in the obtained resin sheet and the circuit board (copper laminate or the like), there is no occurrence of a phenomenon in which the characteristics exhibit local differences due to phase separation or the like, and it is necessary to exhibit a certain performance in any part, and therefore, appearance uniformity is required.

[0264] Here, the diameter of the through hole of the circuit board is preferably 0.1 to 0.5 mm, and the depth is preferably 0.1 to 1.2 mm, in which range resin filling can be performed. In the case where both surfaces of the circuit board are laminated, it is desirable to fill the through hole by about 1 / 2.

[0265] As a specific method of manufacturing the aforementioned resin sheet, a method in which the aforementioned varnished resin composition is coated on the surface of a support film (Y) after the organic solvent is adjusted, and the organic solvent is further dried by heating, blowing hot air, or the like to form a resin composition layer (X) can be exemplified.

[0266] As the organic solvent used herein, a ketone such as acetone, methyl ethyl ketone, cyclohexanone, an acetic acid ester such as ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, carbitol acetate, a carbitol such as butyl carbitol, an aromatic hydrocarbon such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like is preferably used. In addition, it is preferable to use the same at a ratio of 30 to 60 mass% of non-volatile matter.

[0267] In addition, the thickness of the aforementioned resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer possessed by the circuit board is in the range of 5 to 70 μm, the thickness of the aforementioned resin composition layer (X) is preferably in the range of 10 to 100 μm. In addition, the aforementioned resin composition layer (X) in the present embodiment can be protected by a protective film to be described later. By being protected by the protective film, the attachment of dust and the like to the surface of the resin composition layer and scratches on the surface of the resin composition layer can be prevented.

[0268] The aforementioned support film and protective film can be exemplified by polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonates, polyimides, and metal foils such as release paper or copper foil, aluminum foil, and the like. In addition, the support film and the protective film can be subjected to MAD treatment, corona treatment, and release treatment. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 150 μm, more preferably 25 to 50 μm. In addition, the thickness of the protective film is preferably in the range of 1 to 40 μm.

[0269] The aforementioned support film (Y) is peeled after being laminated to the circuit board or after the formation of the insulating layer by heating and hardening. By peeling the support film (Y) after the resin composition layer constituting the resin sheet is heated and hardened, the attachment of dust and the like during the hardening step can be prevented. In the case where peeling is performed after hardening, the support film is subjected to release treatment in advance.

[0270] In addition, a multilayer printed circuit board can be manufactured from the resin sheet obtained according to the foregoing. For example, in the case where the foregoing resin composition layer (X) is protected with a protective film, after peeling these, the layer (X) of the foregoing resin composition is laminated on one side or both sides of a circuit board in a manner to directly contact the circuit board by, for example, a vacuum lamination method. The method of lamination can be batch type or continuous type using a roll press. Furthermore, as needed, the resin sheet and the circuit board can be heated (preheated) as needed before lamination is performed. The conditions of lamination are preferably such that the pressure bonding temperature (laminating temperature) is set to 70 to 140°C, the pressure bonding pressure is set to 1 to 11 kgf / cm 2 (9.8 x 10 4 to 107.9 x 10 4 N / m 2 ), and lamination is performed under reduced pressure at an air pressure of 20 mmHg (26.7 hPa) or less.

[0271] Furthermore, a semiconductor device can be manufactured using the curable resin composition of the present embodiment. As the semiconductor device, for example, DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (thin quad flat package), and the like can be cited.

[0272] The curable resin composition of the present embodiment and the cured product thereof can be used in a wide range of fields. Specifically, it can be used for various purposes such as molding materials, adhesives, composite materials, paints, and the like. Since the cured product of the curable resin composition described in the present embodiment exhibits excellent heat resistance and dielectric properties, it is preferably used for sealing materials for semiconductor elements, sealing materials for liquid crystal display elements, sealing materials for organic EL elements, composite materials for lightweight high-strength structural materials such as electrical and electronic elements and carbon fiber reinforced plastics, glass fiber reinforced plastics, and the like, 3D printing, and the like.

[0273] [Examples]

[0274] Next, the present application is more specifically described by examples. Hereinafter, parts are mass parts unless otherwise specified. However, the present application is not limited to these examples.

[0275] The various analysis methods used in the examples are described below.

[0276] <Weight average molecular weight (Mw), number average molecular weight (Mn), GPC area percentage in the total amount of the compound of the compound of the foregoing formula (1) in which n is 1>

[0277] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated by polystyrene conversion using a polystyrene standard solution.

[0278] GPC: On-line degassing device (DGU-20A3R), binary liquid-chromatograph pump (LC-20AD), automatic injector (SIL-20AHT), differential refractive index detector (RID-20A), column oven (CTO-20A), system controller (CBM-20A) (all manufactured by Shimadzu Corporation)

[0279] Column: Shodex KF-603 x 1, KF-602.5 x 1, KF-602 x 1, KF-601 x 1 (all manufactured by Showa Denko K.K.)

[0280] Guard column: Shodex KF-G 4A (manufactured by Showa Denko K.K.)

[0281] Combined eluate: Tetrahydrofuran

[0282] Flow rate: 1.5 ml / min.

[0283] Column temperature: 40°C

[0284] Detection: RI (differential refractive index detector)

[0285] The slice data of the compound corresponding to n = 1 in formula (1) was obtained, and the ratio (area percentage) of the area of the slice data of the compound corresponding to n = 1 in formula (1) to the sum of the areas (time integral values of signal values) of the slice data of the compounds represented by formula (1) was calculated.

[0286] <Content rate of compounds represented by formulae (2) to (4)>

[0287] HP-LC: Binary liquid-chromatograph pump (LC-20AB), on-line degassing device (DGU-20A3), automatic injector (SIL-20A), column oven (CTO-20A), system controller (CBM-20A), photodiode array detector (SPD-M20A) (all manufactured by Shimadzu Corporation)

[0288] Column: ODS-2 (manufactured by GL Sciences)

[0289] Combined eluate: Tetrahydrofuran: water = 3: 1 (no gradient)

[0290] Flow rate: 0.5 ml / min.

[0291] Column temperature: 40°C

[0292] Detection: PDA (photodiode array detector)

[0293] Detector: 274 nm

[0294] From the chromatograms obtained by high performance liquid chromatography (HP-LC), calculate the sum of the peak areas (α) of the compounds shown in formulas (2) to (4), and the peak area (β) of the compound with n=1 in formula (1), and calculate (α / β).

[0295] <Structural Analysis>

[0296] LC-MS: Ultra-high performance liquid chromatography (UHPLC) system (Ultimate3000), mass analyzer (Q-Exactive (registered trademark)) (both manufactured by Thermo Fisher Scientific).

[0297] Column: ODS-2 (manufactured by GL Sciences)

[0298] Combined eluent: tetrahydrofuran: water = 3:1 (no gradual change)

[0299] Flow rate: 0.5 ml / min.

[0300] Ionization mode: ESI

[0301] Mass range: m / z = 150-2000

[0302] [Synthesis example 1]

[0303] A vacuum pump and a base trap were installed in a flask equipped with a thermometer, cooling pipe, and stirrer. 370.1 parts of (2-bromoethyl)benzene (manufactured by Tokyo Chemical Co., Ltd.), 175.1 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Co., Ltd.), and 27.3 parts of methanesulfonic acid (manufactured by Tokyo Chemical Co., Ltd.) were added to the flask. The generated hydrogen chloride was collected using the base trap, and the mixture was reacted at 130°C for 6 hours. 50 parts of methanol and 700 parts of cyclohexane were added, and the mixture was neutralized with 56.8 parts of a 30% sodium hydroxide aqueous solution. The organic layer was then washed five times with 100 parts of water. Under reduced pressure, the solvent and excess (2-bromoethyl)benzene were distilled off to obtain 380 parts (Mn: 938, Mw: 1290) of a compound (BEB-1) having the (2-bromoethyl)benzene structure shown in formula (6) below, which is a liquid resin. The GPC diagram of the obtained compound is shown in [the diagram]. Figure 1 The average value n of the repeating units n, calculated based on the area percentage of the GPC chart. ave The value is 2.2. Furthermore, the ratio (area percentage) of the area of ​​the compound with the structure n=1 in Equation (6) to the sum of the areas of the compounds with the structure shown in Equation (6) in the GPC chart is 45%.

[0304]

[0305] [Example 1]

[0306] In a flask equipped with a thermometer, a cooling tube, a stirrer, 300 parts of BEB-1 obtained in Synthesis Example 1, 245 parts of toluene, 735 parts of dimethylsulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide radical, and 146.4 parts of 50 wt% sodium hydroxide aqueous solution were added, and continuously reacted at 40°C for 6 hours. 100 parts of water was added, and the organic layer was washed, and then the organic layer was returned to the reaction vessel. 735 parts of dimethylsulfoxide, 9.8 parts of 50 wt% sodium hydroxide aqueous solution were added, and reacted again at 40°C for 1 hour, 1050 parts of toluene was added, and the organic layer was repeatedly washed with 100 parts of water until the waste water became neutral. The concentration was performed under reduced pressure using an evaporator, and 180 parts of a compound having two or more styrene structures in the molecule shown in the following formula (7) (O-1) was obtained. The GPC chart of the obtained compound is shown in Figure 2 In addition, the GPC chart of the obtained compound is shown in 1 H-NMR data (deuterated chloroform) is shown in Figure 3 In the GPC chart, the average value n of the repeating unit n calculated from the area percentage of the GPC chart was 2.3. In addition, the ratio (area percentage) of the area of the compound having the structure of n = 1 in formula (7) to the total of the areas of the compounds having the structures shown in formula (7) in the GPC chart was 40% (the average molecular weight of the resin component was Mn: 803, Mw: 1190). The LC-MS chart is shown in 1 H-NMR chart was observed at 5.10-5.30 ppm, 5.50-5.85 ppm, and 6.60-6.80 ppm. The average value n of the repeating unit n calculated from the area percentage of the GPC chart was 2.3. In addition, the ratio (area percentage) of the area of the compound having the structure of n = 1 in formula (7) to the total of the areas of the compounds having the structures shown in formula (7) in the GPC chart was 40% (the average molecular weight of the resin component was Mn: 803, Mw: 1190). The LC-MS chart is shown in ave was 2.3. In addition, the ratio (area percentage) of the area of the compound having the structure of n = 1 in formula (7) to the total of the areas of the compounds having the structures shown in formula (7) in the GPC chart was 40% (the average molecular weight of the resin component was Mn: 803, Mw: 1190). The LC-MS chart is shown in Figure 4 The HP-LC chart is shown in Figure 5 The compounds V to Y shown in Table 1 (the representative structural formula is described in Table 1) were detected by LC-MS analysis. In the compound W, the positions of the 2-phenylethanol structure and the styrene structure are not particularly ordered. In the compound X, the positions of the 2-phenylethanol structure, the styrene structure, and the 2-phenylacetaldehyde structure are not particularly ordered. In the compound Y, the positions of the 2-phenylethanol structure and the ethylbenzene structure are not particularly ordered, and the benzyl group can be bonded to any aromatic ring.

[0307]

[0308] [Table 1]

[0309]

[0310] [Example 2]

[0311] In a flask equipped with a thermometer, cooling pipe, and stirrer, 300 parts of BEB-1 obtained in Synthesis Example 1, 245 parts of toluene, 735 parts of dimethyl sulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide free radical, and 107.4 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted continuously at 40°C for 6 hours. 100 parts of water were added, and the organic layer was washed and returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted again at 40°C for 1 hour. 1050 parts of toluene were added, and the organic layer was repeatedly washed with 100 parts of water until the wastewater was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of compound (O-2) having more than two styrene structures within the molecule as shown in the aforementioned formula (7). The GPC diagram of the obtained compound is shown in [the diagram]. Figure 6 The average value n of the repeating units n, calculated based on the area percentage of the GPC chart. ave The value is 2.4. Furthermore, the ratio (area percentage) of the area of ​​compounds with a structure where n is 1 in formula (7) to the total area of ​​compounds with the structure shown in formula (7) in the GPC graph is 41% (the average molecular weight of the resin components is Mn: 799, Mw: 1297). The HP-LC graph is represented as follows: Figure 7 .

[0312] [Example 3]

[0313] In a flask equipped with a thermometer, cooling pipe, and stirrer, 300 parts of BEB-1 obtained in Synthesis Example 1, 375 parts of toluene, 1125 parts of dimethyl sulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide free radical, and 146.4 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted continuously at 40°C for 6 hours. 100 parts of water were added, and the organic layer was washed and returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted again at 40°C for 1 hour. 1050 parts of toluene were added, and the organic layer was repeatedly washed with 100 parts of water until the wastewater was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of compound (O-3) having more than two styrene structures within the molecule as shown in the aforementioned formula (7). The GPC diagram of the obtained compound is shown in [the diagram]. Figure 8 The average value n of the repeating units n, calculated based on the area percentage of the GPC chart. ave The value is 2.3. Furthermore, the ratio (area percentage) of the area of ​​compounds with a structure where n is 1 in formula (7) to the total area of ​​compounds with the structure shown in formula (7) in the GPC graph is 35% (the average molecular weight of the resin components is Mn: 834, Mw: 1170). The HP-LC graph is represented as follows: Figure 9 .

[0314] [Example 4]

[0315] In a flask equipped with a thermometer, cooling pipe, and stirrer, 300 parts of BEB-1 obtained in Synthesis Example 1, 245 parts of toluene, 735 parts of dimethyl sulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide free radical, and 146.4 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted continuously at 25°C for 6 hours. 100 parts of water were added, and the organic layer was washed and returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of 50wt% sodium hydroxide aqueous solution were added, and the mixture was reacted again at 25°C for 1 hour. 1050 parts of toluene were added, and the organic layer was repeatedly washed with 100 parts of water until the wastewater was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of compound (O-4) having more than two styrene structures within the molecule as shown in the aforementioned formula (7). The GPC diagram of the obtained compound is shown in [the diagram]. Figure 10 The average value n of the repeating units n, calculated based on the area percentage of the GPC chart. ave The value is 2.5. Furthermore, the ratio (area percentage) of the area of ​​compounds with a structure where n is 1 in formula (7) to the total area of ​​compounds with the structure shown in formula (7) in the GPC graph is 41% (the average molecular weight of the resin components is Mn: 802, Mw: 1291). The HP-LC graph is represented as... Figure 11 .

[0316] [Comparative Synthesis Example 1]

[0317] A vacuum pump and an alkali trap were installed in a flask equipped with a thermometer, cooling pipe, and stirrer. 296 parts of (2-bromoethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 70 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.4 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the flask. The generated hydrogen chloride was collected using the alkali trap, and the mixture was reacted at 130°C for 6 hours. 50 parts of methanol and 700 parts of cyclohexane were added, and the mixture was neutralized with 26.8 parts of a 30% sodium hydroxide aqueous solution. The organic layer was then washed five times with 100 parts of water. Under reduced pressure, the solvent and excess (2-bromoethyl)benzene were distilled off to obtain 171 parts (Mn: 793, Mw: 970) of a compound (BEB-2) having the (2-bromoethyl)benzene structure shown in formula (6) above, which was obtained as a liquid resin. The GPC diagram of the obtained compound is shown in [the diagram]. Figure 12 The average value n of the repeating units n, calculated based on the area percentage of the GPC chart. ave The value is 1.6. Furthermore, the ratio (GPC area percentage) of the area of ​​the compound with the structure n=1 in formula (6) to the sum of the areas of the compounds with the structure shown in formula (6) is 65%.

[0318] [Comparative Synthesis Example 2]

[0319] In a flask equipped with a thermometer, a cooling tube, and a stirrer, BEB-2 obtained in Comparative Synthesis Example 1, 22 parts, toluene, 50 parts, dimethyl sulfoxide, 150 parts, water, 15 parts, and sodium hydroxide, 5.4 parts, were added, and a continuous reaction was performed at 40°C for 6 hours. Toluene, 100 parts, was added, and the organic layer was repeatedly washed with water, 100 parts, until the waste water became neutral. Concentration was performed under reduced pressure using an evaporator, and a compound having two or more styrene structures in the molecule represented by the aforementioned formula (7) (O-5), 12.5 parts, was obtained. The GPC chart of the obtained compound is shown in Figure 13 . The average value n of the repeating unit n calculated from the area percentage of the GPC chart was n ave = 2.2. Furthermore, the ratio of the area of the compound having the structure in which n in formula (7) is 1 to the total of the areas of the compounds having the structures represented by formula (7) (GPC area percentage) in the product was 65% (the average molecular weight of the resin component was Mn: 624, Mw: 778). The HP-LC chart is shown in Figure 14 .

[0320] As the molecular weight data of the compounds O-1 to O-5, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the area percentage of the compound in which n in formula (1) is 1 as "n = 1 content (GPC area %)", the total of the peak areas of the compounds represented by formulae (2) to (4) in the chromatogram obtained by HPLC as "total of the contents of the compounds of V to Y in each compound (HP-LC area)", the peak area β of the compound in which n in formula (1) is 1 as "n = 1 content (HP-LC area)", and the value of α divided by β (α / β) are shown in Table 2.

[0321] [Table 2]

[0322]

[0323] [Examples 5 to 8, Comparative Example 1]

[0324] <Stability Test after Solvent Dissolution>

[0325] After 1.2 g of each of the compounds O-1 to O-5 and 0.8 g of toluene were prepared in a 5 mL glass sample bottle, a 60 wt% toluene solution of each of the compounds was prepared by stirring at 25°C at a rotation speed of 100 rpm for 1 hour using a roll mixer (MIX-ROTAR VMR-5: manufactured by AS ONE Corporation). The obtained solution was stored in a freezer at -18°C, and after 10 minutes, the sample was taken out and evaluated according to the following evaluation criteria. The results are shown in Table 3.

[0326] • Crystallization with no precipitation: O

[0327] • Crystallization with precipitation: X

[0328] <Dielectric constant test and dielectric loss tangent test>

[0329] The compounds O-1 to O-5 were vacuum-pressed while being held with a mirror copper foil (T4X: manufactured by Fukuda Metal Foil & Powder Co., Ltd.), and hardened at 220°C for 2 hours. Thereafter, using a laser cutting machine, they were cut into a sample size of 1.7 mm in width x 100 mm in length x 0.2 mm in thickness, and tested by a cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by AET (Stock) Co., Ltd. The evaluation results are shown in Table 3.

[0330] [Table 3]

[0331]

[0332] According to the results of Table 3, it was confirmed that Examples 5 to 8 have excellent solvent-solubility-after-stability while having excellent dielectric properties.

[0333] This application is based on Japanese Application Patent No. 2022-54487 filed on March 29, 2022.

Claims

1. A compound represented by the following formula (1), wherein the compound having n = 1 in the formula (1) is not more than 50% in terms of GPC area percentage in the total amount of the compound. In formula (1), the plurality of R each independently represents a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group; p = 0, q = 0, r = 0; n is a number of repetitions, and the average value of n ave The value calculated from the number average molecular weight (Mn) determined by GPC of the compound represented by formula (1) satisfies 1.1 ≤ n ave ≤ 10; The GPC area percentage is a ratio (area percentage) of the area (time integral value of signal value) of the slice data corresponding to the compound having n = 1 in the formula (1) to the sum of the areas (time integral value of signal value) of the slice data corresponding to the compounds represented by the formula (1), which is calculated by obtaining the slice data from a chromatogram obtained by GPC.

2. The compound of claim 1, wherein, The value of α / β, which is the sum α of the peak areas of the compounds represented by the following formulas (2) to (4) divided by the peak area β of the compound having n = 1 in the formula (1), is not more than 0.10; In the formula (2), each of a plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group; s = 0, t = 0. In the formula (3), each of a plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group; each of a plurality of A's independently is any one of the following formulas (3-a) to (3-c) ; s = 0, t = 0. In the formulas (3-a) to (3-c), * indicates a position bonded to the aromatic ring of the compound of the formula (3). In the formula (4), each of a plurality of R's independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group; each of a plurality of B's independently is the following formula (4-d) or (4-e) ; D is the following formula (4-f) ; s = 0, t = 0; one of the five m's in the formula (4) is 1, and the remaining four are 0. In the formulas (4-d) to (4-f), * indicates a position bonded to the aromatic ring of the compound of the formula (4).

3. The compound of claim 1 or 2, wherein, The compound represented by the formula (1) is derived from a compound represented by the following formula (5) ; In formula (5), a plurality of R exist independently and represent a hydrocarbon group having a carbon number of 1 to 10 or a halogenated alkyl group; p = 0, q = 0, r = 0, n is a repeating number, and the average value n ave complies with 1.1 ≤ n ave ≤ 10; and X represents a halogen atom.

4. A mixture comprising the compound according to claim 1 or 2 and a polymerization inhibitor.

5. A curable resin composition comprising the compound according to claim 1 or 2.

6. The curable resin composition according to claim 5, comprising any one or more of a polyphenylene ether compound, a polybutadiene and a modified product thereof, a polystyrene and a modified product thereof.

7. The curable resin composition according to claim 5, comprising a radical polymerization initiator.

8. A cured product obtained by curing the compound according to claim 1 or 2.

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