Active ester resins, resin compositions, cured products and uses thereof, and resins containing phenolic hydroxyl groups

Abstract

The present invention provides active ester resins, resin compositions, cured products, and uses thereof, and resins containing phenolic hydroxyl groups. According to the present disclosure, it is possible to provide active ester resins in which the adjustment range of the functional group equivalent is wide and the relative dielectric constant and the dielectric loss tangent of the cured product are low, an epoxy resin composition containing the active ester resin, a cured product obtained by curing the epoxy resin composition, a printed wiring board, a build-up film, and a semiconductor sealing material. An active ester resin obtained by reacting a resin containing phenolic hydroxyl groups (A) having a structure represented by formula (x) with an aromatic (poly)carboxylic acid or an acid halide thereof (B).

Description

Technical Field

[0001] This invention relates to reactive ester resins, epoxy resin compositions containing the reactive ester resins, and cured products obtained by curing the epoxy resin compositions. Background Technology

[0002] In recent years, the increasing sophistication of network services and the high performance and functionality of information terminal equipment and sensors have driven the expansion of information processing capacity and the acceleration of data processing speed. Since higher radio wave frequencies can transmit more information, the utilization of high-frequency bands above tens of GHz has been studied. For components such as circuit boards and antennas used in corresponding equipment, materials with low dielectric loss corresponding to high-frequency bands are required.

[0003] Epoxy resin compositions containing epoxy resin and curing agents exhibit high heat resistance and insulation properties upon curing, and are therefore widely used in electronic components such as semiconductors and circuit boards. As curing agents, reactive ester resins with intramolecular ester structures have been reported (Patent Document 1). Epoxy resin compositions using reactive ester resins can produce cured products with lower relative dielectric constants and dielectric loss tangents compared to those using conventional curing agents such as phenolic varnish resins. However, the dielectric properties of cured products using known reactive ester resins are insufficient.

[0004] Furthermore, when used as a resin composition, the curing agent preferably allows for arbitrary adjustment of the functional group equivalent. A curing agent that can be adjusted without significant design changes, based on desired physical properties such as the glass transition temperature, dielectric properties, mechanical properties, viscosity of the cured product, and compatibility with other components, is beneficial for optimizing the composition of the resin composition. However, with known reactive ester-type curing agents, adjusting the functional group equivalent requires adjusting the ratio of the phenolic hydroxyl-containing resin (A) to the aromatic (poly)carboxylic acid or its acid halide (B), or significantly altering the molecular structure of the phenolic hydroxyl-containing resin (A) by introducing substituents. Changing the ratio of the phenolic hydroxyl-containing resin (A) to the aromatic (poly)carboxylic acid or its acid halide (B) significantly alters the softening point of the reactive ester resin and its compatibility with the resin composition, thus narrowing the range of adjustable functional group equivalents while maintaining easily manageable resin properties. Furthermore, when substituents are introduced into a resin (A) containing phenolic hydroxyl groups, the physical properties of the reactive ester resin and the characteristics of the cured product change significantly. Therefore, the adjustable range of functional group equivalent is narrow, resulting in low versatility. Thus, there is a need to develop an epoxy resin curing agent that allows for a wide adjustment range of functional group equivalent without significant changes to the molecular structure, and provides cured products exhibiting low relative permittivity and dielectric loss tangent.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-235165 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The problem to be solved by the present invention is to provide an active ester resin with a wide range of functional group equivalent adjustment and low relative permittivity and dielectric loss tangent of the cured product, an epoxy resin composition containing the active ester resin, a cured product obtained by curing the epoxy resin composition, a printed wiring substrate, a layering film, and a semiconductor sealing material.

[0010] Methods for solving problems

[0011] To address the aforementioned issues, the inventors conducted in-depth research and, as a result, developed an active ester resin with a specific structure. Specifically, the present invention provides an active ester resin obtained by reacting a phenolic hydroxyl-containing resin (A) with an aromatic (poly)carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl-containing resin (A) has a structure represented by formula (x), and provides an epoxy resin composition containing this active ester resin and a cured product obtained by curing the epoxy resin composition.

[0012] Invention Effects

[0013] The active ester resin of the present invention can widely adjust the functional group equivalent without significantly changing the molecular structure. When the cured product is formed, it has a relatively low dielectric constant and dielectric loss tangent, and is therefore suitable as a resin composition material for printed wiring substrates, extension films and semiconductor sealing materials. Attached Figure Description

[0014] Figure 1 This is the GPC diagram of the active ester resin (I-1) described in Example 1.

[0015] Figure 2 This is the GPC diagram of the active ester resin (I-2) described in Example 2.

[0016] Figure 3 This is the GPC diagram of the active ester resin (I-3) described in Example 3.

[0017] Figure 4 This is the GPC diagram of the active ester resin (I-4) described in Example 4.

[0018] Figure 5 This is the GPC diagram of the active ester resin (I-5) described in Example 5.

[0019] Figure 6 This is the GPC diagram of the active ester resin (I-6) described in Example 6.

[0020] Figure 7 This is the GPC diagram of the active ester resin (I-7) described in Example 7.

[0021] Figure 8 This is the GPC diagram of the active ester resin (I-8) described in Example 8.

[0022] Figure 9 This is the GPC diagram of the active ester resin (I-9) described in Example 9.

[0023] Figure 10 This is the GPC diagram of the active ester resin (I-10) described in Example 10.

[0024] Figure 11 This is the GPC diagram of the active ester resin (I-11) described in Example 11. Detailed Implementation

[0025] The present invention provides an active ester resin, which is an active ester resin obtained by reacting a phenolic hydroxyl-containing resin (A) with an aromatic (poly)carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl-containing resin (A) has a structure represented by the following formula (x).

[0026] [Chemistry 1]

[0027]

[0028] (In the formula, * indicates the bonding position, Ra represents a group selected from aliphatic hydrocarbon groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms, aryl groups with 3 to 20 carbon atoms, and aralkyl groups with 4 to 20 carbon atoms. When there are multiple Ra, they can be the same or different, and k represents an integer from 0 to 3.)

[0029] In the aforementioned active ester resins, from the viewpoint of compatibility with other components when added to the resin composition and solubility in solvents, resins (A) containing phenolic hydroxyl groups are preferred, and are represented by the following general formula (A1).

[0030] [Chemistry 2]

[0031]

[0032] (where A is in the formula) 1 and A 2Each of the following independently represents a substituted hydrocarbon ring or heterocycle with 3 to 18 carbon atoms; Ra represents a group selected from aliphatic hydrocarbon groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms, aryl groups with 3 to 20 carbon atoms, and aralkyl groups with 4 to 20 carbon atoms; when multiple Ra are present, they may be the same or different; k represents an integer from 0 to 3; n is the average number of repeating units, representing a value from 0.5 to 40. More preferably, a resin (A) containing phenolic hydroxyl groups is represented by the following general formula (A11).

[0033] [Chemistry 3]

[0034]

[0035] (where A is in the formula) 11 and A 21 Ra represents either a hydrocarbon ring with 6 to 18 substituted carbon atoms or a heterocycle with 3 to 12 substituted carbon atoms, each independently representing a hydrocarbon ring with 6 to 18 substituted carbon atoms. 1 Ra represents a group selected from straight-chain or branched alkyl groups having 1 to 5 carbon atoms, straight-chain or branched alkenyl groups having 1 to 5 carbon atoms, straight-chain or branched alkoxy groups having 1 to 5 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, aryl groups having 4 to 10 carbon atoms, and aralkyl groups having 5 to 11 carbon atoms. 1 When multiple units exist, they can be the same or different, where k1 represents 0, 1, or 2, and n1 is the average number of repeating units, representing a value from 1 to 30. Further preferably, the resin (A) containing phenolic hydroxyl groups is represented by the following general formula (A111).

[0036] [Chemistry 4]

[0037]

[0038] (where A is in the formula) 111 and A 211 Each can independently represent a substituted benzene ring or a substituted naphthalene ring, Ra 11 Ra represents a group selected from straight-chain or branched alkyl groups having 1 to 5 carbon atoms, straight-chain or branched alkenyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 11 carbon atoms. 11 When multiple units exist, they can be the same or different. k11 represents 0 or 1, and n11 is the average number of repeating units, representing a value from 1 to 20. A resin (A) containing phenolic hydroxyl groups is particularly preferred and is represented by the following general formula (A1111).

[0039] [Chemistry 5]

[0040]

[0041] (where A is in the formula)1111 and A 2111 Each of the groups independently represents a group selected from formulas (a-1) to (a-4) below.

[0042] [Chemistry 6]

[0043]

[0044] (In the formula, * indicates the bonding position.), n111 is the average number of repeating units, representing a value from 2 to 15.), The most preferred resin (A) containing phenolic hydroxyl groups is represented by the following general formula (A11111).

[0045] [Chemistry 7]

[0046]

[0047] (In the formula, HO-A 11111 and A 21111 The -OH group represents a group selected independently from formulas (a-11) to (a-41) below.

[0048] [Chemistry 8]

[0049]

[0050] (In the formula, * represents the bonding position.) n1111 is the average number of repeating units, representing a value from 3 to 12.

[0051] When adding the active ester resin of the present invention to an epoxy resin composition to produce a resin board, especially when a balance between low dielectric loss tangent and glass transition temperature is important, the phenolic hydroxyl-containing resin (A) is particularly preferably a resin represented by the following formula (A11112).

[0052] [Chemistry 9]

[0053]

[0054] (In the formula, n1112 is the average number of repeating units, representing a value from 3 to 12.) Furthermore, when considering the low softening point and low viscosity of the phenolic hydroxyl-containing resin (A), the phenolic hydroxyl-containing resin (A) is particularly preferred to be a resin represented by the following formula (A11113).

[0055] [Chemistry 10]

[0056]

[0057] (In the formula, n1113 is the average number of repeating units, representing a value from 3 to 12.)

[0058] In this specification, a group whose bonding position is not fixed to any atom constituting the ring refers to a group that can bond to any one of the substituted cyclic atoms in the ring. For example, in the structural formula represented by formula (a-11), * can bond to any one of the seven substituted cyclic carbon atoms in the naphthalene ring contained in 1-naphthol. Furthermore, in the structural formula represented by formula (a-1), the two * can bond to different cyclic carbon atoms among the eight substituted cyclic carbon atoms in the naphthalene ring.

[0059] In the reactive ester resin of the present invention, the aromatic (poly)carboxylic acid or its acid halide (B) is not particularly limited in its specific structure, as long as it is an aromatic compound capable of reacting with the phenolic hydroxyl group of the resin (A) containing a phenolic hydroxyl group to form an ester bond. Any compound can be used. Specific examples include, for instance, isophthalic acid, terephthalic acid, and other phenyl dicarboxylic acids, trimellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, their acid halides, and compounds in which the aforementioned aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc., are substituted on their aromatic nuclei. Examples of acid halides include, for instance, acyl chlorides, acyl bromides, acyl fluorides, and acyl iodides. These can be used individually or in combination of two or more. From the perspective of creating a reactive ester resin with high reactivity and excellent curability, isophthalic acid, terephthalic acid, and other phenyl dicarboxylic acids or their acid halides are preferred.

[0060] The active ester resin of the present invention exhibits a low relative permittivity and dielectric loss tangent. However, from the viewpoint of improving the heat resistance, mechanical strength, and adhesion to copper foil and other physical properties of the cured product, it can also be a resin obtained by reacting a phenolic hydroxyl-containing resin (A), an aromatic (poly)carboxylic acid or its acid halide (B), and a compound (C) that is a phenolic hydroxyl-containing compound and different from the phenolic hydroxyl-containing resin (A). In this case, the specific structure of the phenolic hydroxyl-containing compound (C) is not particularly limited, as long as it is a compound or resin that can bring about the desired physical properties; it can be any compound.

[0061] As for the compound (C) containing a phenolic hydroxyl group, specifically, examples of compounds having one phenolic hydroxyl group include aromatic monohydroxyl compounds such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, and β-naphthol. From the viewpoint of obtaining a low dielectric loss tangent of the cured product, α-naphthol, β-naphthol, o-phenylphenol, or p-phenylphenol are preferred.

[0062] Furthermore, as for the compound (C) containing phenolic hydroxyl groups, specifically, examples of compounds having two or more phenolic hydroxyl groups include resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthodiol, 2,6-naphthodiol, 2,3-naphthodiol, 2,7-naphthodiol, 1,4-naphthodiol, 3,3',5,5'-tetramethylbisphenol F, 3,3',5,5'-tetramethylbiphenol, and other aromatic dihydroxy compounds; 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4'-trihydroxybenzophenone, triphenolmethane, and other aromatic trihydroxy compounds; 2,2',4,4'-tetrahydroxybenzophenone, 1,1,2,2-tetraphenolethane, etc. From the viewpoint of obtaining a low dielectric loss tangent of the cured product, bisphenol A, bisphenol F, bisphenol S, 3,3',5,5'-tetramethylbisphenol F or 3,3',5,5'-tetramethylbiphenol are preferred.

[0063] Specifically, as the active ester resin of the present invention, resins represented by the following formulas (E-1) to (E-8) can be cited as examples.

[0064] [Chemistry 11]

[0065]

[0066] [Chemistry 12]

[0067]

[0068] [Chemistry 13]

[0069]

[0070] (In the formula, k is the average number of repeating units, representing a value from 0.5 to 40, and l is the average number of repeating units, representing a value from 0.5 to 10.)

[0071] The active ester resin of the present invention can be manufactured by the following method.

[0072] (Preparation Method 1) Manufacturing of an active ester resin represented by the following formula (E-5)

[0073] [Chemistry 14]

[0074]

[0075] (In the formula, k is the average number of repeating units, representing a value from 0.5 to 40, and l is the average number of repeating units, representing a value from 0.5 to 10.)

[0076] By reacting a compound represented by formula (M1) with a compound containing phenolic hydroxyl groups represented by formula (M2) in the presence of an acid, for example, a resin containing phenolic hydroxyl groups represented by formula (M3) can be obtained. Examples of acids include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid; Lewis acids such as aluminum chloride, boron trifluoride, zinc chloride, and ferric chloride; and solid acids such as activated clay. When the theoretical amount of the obtained resin containing phenolic hydroxyl groups is set to 100 parts by mass, the amount of acid used is preferably 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less. When using a solid acid, when the theoretical amount of the obtained resin containing phenolic hydroxyl groups is set to 100 parts by mass, it is preferably 0.01 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 50 parts by mass or less, and particularly preferably 1 part by mass or more and 20 parts by mass or less.

[0077] The reaction between the compound represented by formula (M1) and the compound containing a phenolic hydroxyl group represented by formula (M2) can be carried out in a solvent-free environment or in a solvent. Examples of solvents include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, benzene, toluene, xylene, chlorobenzene, cyclohexane, and dichloromethane. From the viewpoint of reactivity and ease of post-processing, toluene or xylene is preferred.

[0078] The reaction can be carried out by mixing the compound represented by formula (M1), the phenolic hydroxyl-containing compound represented by formula (M2), and a reaction solvent, followed by the addition of an acid. Alternatively, the compound represented by formula (M1), an acid, and a reaction solvent can be mixed, allowing the compound represented by formula (M1) to react alone, before adding the phenolic hydroxyl-containing compound represented by formula (M2). The reaction temperature is not particularly limited, but from the viewpoint of the viscosity and solubility of the resulting phenolic hydroxyl-containing resin represented by formula (M3), it is preferably 50°C or higher and 250°C or lower, more preferably 80°C or higher and 200°C or lower, and particularly preferably 110°C or higher and 150°C or lower. After the reaction, the acid and any remaining unreacted phenolic hydroxyl-containing compound represented by formula (M2) are removed by neutralization, washing with water, filtration, or decomposition. The target phenolic hydroxyl-containing resin can be separated by general operations such as extraction or distillation. Neutralization and washing can be carried out using conventional methods, such as using alkaline substances like sodium hydroxide, potassium hydroxide, sodium carbonate, or ammonia as neutralizing agents. Alternatively, after the reaction, the remaining unreacted compound containing phenolic hydroxyl groups (represented by formula (M2)) can be used in the next reaction step without removing it.

[0079] The compound represented by formula (M1) can undergo dehydration in the presence of acid to form 1,3-diisopropenylbenzene, and then undergo polymerization, cyclization, or addition reactions with compounds containing phenolic hydroxyl groups. Alternatively, 1,3-diisopropenylbenzene or a 1,3-diisopropenylbenzene precursor other than the compound represented by formula (M1) can be used as a starting material instead of the compound represented by formula (M1).

[0080] Next, the phenolic hydroxyl-containing resin represented by formula (M3) is reacted with, for example, compounds represented by formula (M4) and (M5) in the presence of a base, to obtain the active ester resin represented by formula (E-5). Examples of bases include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Sodium hydroxide and potassium hydroxide can be used in aqueous solution, which is preferred from the perspective of improving productivity.

[0081] The reaction can be carried out in the presence of an organic solvent by mixing a resin containing phenolic hydroxyl groups (M3), a compound (M4), and a compound (M5), and reacting them by continuously or intermittently adding an aqueous solution of a base or the base catalyst. The concentration of the aqueous solution of the base catalyst is preferably in the range of 3.0 to 30% by mass. Examples of organic solvents include toluene, dichloromethane, and chloroform. After the reaction, the base is neutralized and the mixture is washed with water, thereby obtaining the active ester resin represented by formula (E-5).

[0082] The functional group equivalent of the active ester resin of the present invention can be adjusted to a desired value by means of the number of repeating units n of the phenolic hydroxyl-containing resin (A) represented by formula (A1). The number of repeating units n of the phenolic hydroxyl-containing resin (A) can be arbitrarily adjusted by means of the feed ratio of the phenolic hydroxyl-containing compound to 1,3-diisopropenylbenzene or its precursor during the synthesis of the phenolic hydroxyl-containing resin (A).

[0083] In addition to the linear molecular structure specifically illustrated above, the active ester resin of the present invention may also contain a branched molecular structure. When manufacturing the phenolic hydroxyl-containing resin (A) as an intermediate, if a compound capable of multiple substitution such as phenol, o-cresol, α-naphthol, or β-naphthol is used, 1,3-diisopropenylbenzene or its precursor may substitute one or more sites relative to the phenolic hydroxyl-containing compound. When 1,3-diisopropenylbenzene or its precursor is substituted at two or more sites relative to the phenolic hydroxyl-containing compound, the resulting active ester resin has a branched molecular structure.

[0084] Regarding the active ester resin of the present invention obtained in this way, its solubility in organic solvents is increased, making it a suitable material for varnishes for circuit boards. Furthermore, considering the excellent balance of heat resistance, flame retardancy, dielectric properties, and resistance to thermal decomposition, its softening point is preferably 70°C or higher and 200°C or lower.

[0085] When the total number of aromatic ester groups in the molecule is taken as the number of functional groups of the active ester, from the viewpoint of curability and dielectric properties, the functional group equivalent of the active ester resin of the present invention is preferably 50 g / equivalent or more and 5000 g / equivalent or less, more preferably 100 g / equivalent or more and 2000 g / equivalent or less, and particularly preferably 120 g / equivalent or more and 1000 g / equivalent or less.

[0086] From the viewpoints of curability, dielectric properties, and compatibility with other components, the number average molecular weight (Mn) of the active ester resin of the present invention is preferably 300 or more and 6000 or less, more preferably 400 or more and 5000 or less, and particularly preferably 500 or more and 4000 or less.

[0087] <Resin Composition>

[0088] The active ester resin of the present invention functions as a curing agent for epoxy compounds and other compounds. When reacting with epoxy resin, the active ester resin of the present invention can prevent or inhibit the generation of hydroxyl groups, thus yielding a cured product with excellent low dielectric properties, which is useful.

[0089] Specifically, examples of epoxy resins that can be used in combination with the active ester resin of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, bisphenol A phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl phenolic varnish type epoxy resin, and naphthol phenolic varnish type epoxy resin. Naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed phenolic varnish type epoxy resin, naphthol-cresol co-condensed phenolic varnish type epoxy resin, biphenyl-modified phenol type epoxy resin (a polyphenol type epoxy resin in which the phenol skeleton and the biphenyl skeleton are linked by dimethylene groups), biphenyl-modified naphthol type epoxy resin (a polynaphthol type epoxy resin in which the naphthol skeleton and the biphenyl skeleton are linked by dimethylene groups), alkoxy-containing aromatic ring modified phenolic varnish type epoxy resin (a resin in which an aromatic ring containing glycidyl groups and an aromatic ring containing alkoxy groups are linked by formaldehyde), phenylene ether type epoxy resin, naphthylene ether type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, xanthanene type epoxy resin, etc. These can be used individually or in combination of two or more types.

[0090] Among the epoxy resins, those yielding cured products with excellent dielectric properties are preferably phenolic varnish-type epoxy resins, cresol varnish-type epoxy resins, bisphenol A varnish-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, triphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins, biphenyl varnish-type epoxy resins, naphthol varnish-type epoxy resins, naphthol-phenol cocondensed phenolic varnish-type epoxy resins, naphthol-cresol cocondensed phenolic varnish-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, and xanthine-type epoxy resins. Particularly preferred are dicyclopentadiene-phenol addition reaction epoxy resins, naphthol varnish-type epoxy resins, and phenol aralkyl-type epoxy resins. Epoxy resins include: alkyl-biphenyl epoxy resins, alkyl-naphthol epoxy resins, naphthol-phenol co-condensed phenolic varnish epoxy resins, naphthol-cresol co-condensed phenolic varnish epoxy resins, biphenyl-modified phenol epoxy resins (polyphenolic epoxy resins formed by linking the phenol skeleton and the biphenyl skeleton through dimethylene groups), biphenyl-modified naphthol epoxy resins (polynaphthol epoxy resins formed by linking the naphthol skeleton and the biphenyl skeleton through dimethylene groups), alkoxy-containing aromatic ring-modified phenolic varnish epoxy resins (resins formed by linking an aromatic ring containing glycidyl groups and an aromatic ring containing alkoxy groups with formaldehyde), aromatic hydrocarbon formaldehyde resin-modified phenolic resin epoxy resins, and naphthylene ether epoxy resins.

[0091] Commercially available epoxy resins that can be mixed with the reactive ester resin of the present invention include, specifically, EPICLON (registered trademark) 840, EPICLON 840-S, EPICLON 850, EPICLON 850-S, EPICLON EXA-850CRP, EPICLON EXA-830LVP, EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HHH, EPICLON HP-7200H-75M, EPICLON HP-4032SS, EPICLON HP-4032D, EPICLON HP-EXA-4850-150, EPICLON HP-EXA-4850-1000, EPICLON HP-7250, EPICLON HP-4700, and EPICLON... HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON HP-9900-75M, EPICLON HP-9500, EPICLON HP-6000, EPICLON HP-6000L (all manufactured by DIC Corporation), Epotohto (registered trademark) YD-128, Epotohto YD-128G, Epotohto YD-128S, Epotohto YD-128CA, Epotohto YD-134, Epotohto YD-011, Epotohto YD-012, Epotohto YD-013, Epotohto YDF-170, Epotohto YDF-170N, Epotohto YDF-2001, Epotohto YD-8125, Epotohto Epotohto FX-289BEK75, Epotohto FX-1225EK75, Epotohto ST-3000, Epotohto ST-4000D, Epotohto YDC-1312, Epotohto YSLV-70XY, Epotohto YSLV-80XY, Epotohto YSLV-120TE (manufactured by Nippon Steel Chemical Materials Co., Ltd.), jER (registered trademark) 825, jER827, jER 828, jER 834, jER 801N, jER 811, jER 813, jER 816A, jER 819, jER 806, jER806H, jER 807, jER 4005P, jER 4007P, jER 4010P, jER 152, jER 154, jER 157S70, jER1031S, jER 1032H60, jER 604, jER 630, jER 871, jER 872, jER 872X75, jER 890, jERYL6810, jER 1750, jER YX 7700, jER 8000, jER YX8034, jER YL980, jER YL983U, jERYX7400N, jER YX 7105, jER YX 7110 B80, jER YX 7760, jER YX 4000, jER YX 4000H, jER4000 HS, jER YL 6121 HA、jER YL 6677 (manufactured by Mitsubishi Chemical Corporation), NC-3100, NC-3000-L, NC-3000, NC-3000-H, NC-3000-FH-75M, NC-2000-L, XD-1000-2L, XD-1000, XD-1000-H, NC-7000-L, NC-7300-L, EPPN-201, RE-305, RE-306, RE-305S, BR-250H, EPPN-501H, EPPN-501HY, EPPN-502H, FAE-2500, GTR-1800, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc.

[0092] Regarding the proportions of the active ester resin and epoxy resin in the resin composition of the present invention, from the viewpoint of improving curability and the various physical properties of the cured product, the carbonyl group constituting the ester group in the active ester resin is preferably 0.8 equivalents or more and 1.5 equivalents or less relative to 1 equivalent of epoxy groups in the resin composition. From the viewpoint of improving dielectric properties and heat resistance of the cured product while maintaining excellent flame retardancy, a proportion of 0.9 equivalents or more and 1.3 equivalents or less is particularly preferred. When the phenolic hydroxyl group constituting the ester group in the active ester resin has multiple substituents around it or has a large substituent, the reactivity of the phenolic hydroxyl group with the epoxy group becomes lower. Therefore, relative to 1 equivalent of epoxy groups in the resin composition, it is preferable to increase the equivalent of the carbonyl group constituting the ester group in the active ester resin.

[0093] <Other Curing Agents>

[0094] In addition to the above-mentioned active ester resin and epoxy resin, the resin composition of the present invention can also be combined with other epoxy resin curing agents. Examples of other epoxy resin curing agents include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, and phenolic curing agents. Examples of amine-based curing agents include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophorone diamine, imidazole, boron trifluoride-amine complex, and guanidine derivatives. Examples of amide-based curing agents include dicyandiamide and polyamide resins synthesized from linolenic acid dimers and ethylenediamine. Examples of acid anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples of phenolic curing agents include phenol and phenolic resin. Varnish resin, cresol phenolic varnish resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition-type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolpropane resin, tetrahydroxyphenyl ethane resin, naphthol phenolic varnish resin, naphthol-phenol cocondensed phenolic varnish resin, naphthol-cresol cocondensed phenolic varnish resin, biphenyl modified phenolic resin (a polyphenolic resin in which the phenol core is linked by dimethylene groups), biphenyl modified naphthol resin (a polyphenolic resin in which the phenol core is linked by dimethylene groups), aminotriazine modified phenolic resin (a polyphenolic resin in which the phenol core is linked by melamine, benzoguanamine, etc.), etc.

[0095] In particular, from the perspective of flame retardant effect, resins containing a large amount of aromatic skeleton in the molecular structure are preferred. Specifically, phenolic resin, cresol resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol resin, naphthol-phenol cocondensed phenolic resin, naphthol-cresol cocondensed phenolic resin, biphenyl modified phenolic resin, biphenyl modified naphthol resin, and aminotriazine modified phenolic resin are preferred.

[0096] Commercially available epoxy resin curing agents that can be used in combination with the active ester resin of the present invention include, specifically, phenolic curing agents such as PHENOLITE (registered trademark) TD-2131, PHENOLITE TD-2093Y, PHENOLITE TD-2093Y-60M, PHENOLITE TD-2090, PHENOLITE TD-2090-60M, PHENOLITE KA-1160, PHENOLITE KA-1163, PHENOLITE KA-1165, PHENOLITE VH-4150, PHENOLITE VH-4170, PHENOLITE KH-6021, PHENOLITE LF-7911, PHENOLITE LF-6161, PHENOLITE LF-4871, EPICLON HPC-9500-60M, and EPICLON. HPC-9500P-53M, PHENOLITE LA-1356, PHENOLITE LA-3018-50P, PHENOLITE LA-7052, PHENOLITE LA-7054, PHENOLITE LA-7751 (all manufactured by DIC Corporation), SK RESIN HE100C-10, SK RESIN HE100C-15, SK RESIN HE 100C-30, SK RESIN HE200C-07, SK RESIN HE200C-10, SK RESIN HE510-05, SK RESIN HE610C-07, SK RESIN HE910-10, SK RESIN HE910-20 (all manufactured by Air Water Performance Chemical Co., Ltd.), KAYAHARD (registered trademark) GPH-65, KAYAHARD GPH-103, KAYAHARD KTG-105 (manufactured by Nippon Kayaku Co., Ltd.), jER CURE 170 (registered trademark), jER CURE 171N (manufactured by Mitsubishi Chemical Co., Ltd.), Milex XL (registered trademark), Milex RS, Milex RN (manufactured by MITSUI FINE CHEMICALS Co., Ltd.), and ZX-798P (manufactured by Nippon Steel Chemical Materials Co., Ltd.) are used as amine-based curing agents.Examples of anhydride-based curing agents include EPICLON B-065 (manufactured by DIC Corporation), KAYAHARD AA (manufactured by Nippon Kayaku Co., Ltd.), jER CURE ST14, jER CURE YN100, jERCURE SA1, jER CURE TO184, and jER CURE WA (all manufactured by Mitsubishi Chemical Corporation). Examples of anhydride-based curing agents include EPICLON B-4500 MC-C, EPICLON B-4500-C, EPICLON B-4500MC (manufactured by DIC Corporation), HN-2200, MHAC-P (manufactured by Risenok Co., Ltd.), KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd.), jER CURE YH306, and jER CURE YH307 (all manufactured by Mitsubishi Chemical Corporation).

[0097] The other curing agents can be used alone or in combination of two or more.

[0098] Furthermore, the resin composition of the present invention can also be used in conjunction with an active ester resin other than the active ester resin of the present invention as a curing agent for epoxy resin. Examples of active ester resins other than the active ester resin of the present invention include EPICLON (registered trademark) HPC-8000-65T, EPICLON HPC-8000L-65MT, EPICLON HPC-8150-62T, EPICLONEXB-8, and EPICLON NE-V-1100-70T (all manufactured by DIC Corporation).

[0099] <Other thermosetting resins>

[0100] In addition to the active ester resins and epoxy resins detailed above, the resin compositions of the present invention can also incorporate other thermosetting resins. Examples of other thermosetting resins include, for instance, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol phenolic varnish resins, cyanate ester resins, styrene-maleic anhydride resins, diallyl bisphenol, triallyl isocyanurate and other allyl-containing resins, polyphosphate esters, phosphate ester-carbonate copolymers, etc. These other resins can be used alone or in combination of two or more.

[0101] Solvent

[0102] The resin composition of the present invention can be prepared without solvent or may contain a solvent. The solvent has functions such as adjusting the viscosity of the resin composition. Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellolytic agents and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

[0103] The amount of solvent used, relative to the total mass of the resin composition, is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less. From the viewpoint of excellent operability, it is preferable that the amount of solvent used is 10% by mass or more. On the other hand, from the viewpoint of economy, it is preferable that the amount of solvent used is 90% by mass or less.

[0104] <Additives>

[0105] The resin composition of the present invention may contain additives. Examples of additives include curing accelerators, flame retardants, and fillers.

[0106] <Curing Accelerator>

[0107] Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators.

[0108] Examples of phosphorus-based curing accelerators include organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphite compounds such as trimethyl phosphite and triethyl phosphite; ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, butyltetraphenylboronic acid phosphine, tetraphenylphosphine tetraphenylborate, tetraphenylphosphine tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphine thiocyanate, tetraphenylphosphine dicyanamide, butylphenylphosphine dicyanamide, and tetrabutylphosphine decanoate.

[0109] Examples of amine-based curing accelerators include triethylamine, tributylamine, N,N-dimethylaminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene (DBU), and 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN).

[0110] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

[0111] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, and 1-phenylbiguanidine.

[0112] Examples of urea-based curing accelerators include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

[0113] Among the above-mentioned curing accelerators, 2-ethyl-4-methylimidazolium and N,N-dimethylaminopyridine (DMAP) are preferred. It should be noted that the above-mentioned curing accelerators can be used alone or in combination of two or more.

[0114] The amount of curing accelerator used can be appropriately adjusted to obtain the desired curability. It is preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total mixture of the epoxy resin and the reactive ester resin. From the perspective of excellent curability, it is preferable that the amount of curing accelerator used is 0.01 parts by mass or more. On the other hand, from the perspective of excellent insulation reliability, it is preferable that the amount of curing accelerator used is 5 parts by mass or less.

[0115] Flame retardants

[0116] As a flame retardant, there are no particular limitations; examples include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants.

[0117] There are no particular limitations on the inorganic phosphorus-based flame retardants mentioned above, and examples include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and phosphoramide.

[0118] As for the organophosphorus flame retardant mentioned above, there are no particular limitations, and examples include methyl phosphate, ethyl phosphate, isopropyl phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl phosphate, lauryl phosphate, tridecyl phosphate, stearyl phosphate, isostearyl phosphate, oleyl phosphate, butyl pyrophosphate, tetracosyl phosphate, glycolic acid phosphate, methacrylate (2-hydroxyethyl) ester phosphate, etc.; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene. -10-oxides, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxides, diphenylphosphine hydroquinone, diphenylphosphine-1,4-dioxynaphthalene, 1,4-cyclooxyphosphine-1,4-benzenediol, 1,5-cyclooxyphosphine-1,4-benzenediol and other phosphorus-containing phenols, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxides, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxides and other cyclic phosphorus compounds, compounds obtained by reacting the phosphate esters, the diphenylphosphine, the phosphorus-containing phenols with epoxy resins, aldehyde compounds, phenolic compounds, etc.

[0119] There are no particular limitations on the halogen-based flame retardants mentioned above, and examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid, etc.

[0120] The flame retardant can be used alone or in combination of two or more types.

[0121] The amount of flame retardant used relative to 100 parts by weight of epoxy resin is preferably 0.1 parts by weight or more and 50 parts by weight or less, more preferably 1 part by weight or more and 30 parts by weight or less. From the perspective of imparting flame retardancy, the amount of flame retardant used is preferably 0.1 parts by weight or more. On the other hand, from the perspective of imparting flame retardancy while maintaining dielectric properties, the amount of flame retardant used is preferably 50 parts by weight or less.

[0122] <filler>

[0123] As fillers, organic fillers and inorganic fillers can be listed. Organic fillers have functions such as improving elongation and increasing mechanical strength. Inorganic fillers have functions such as reducing thermal expansion coefficient and imparting flame retardancy.

[0124] There are no particular limitations on the organic filler used, and examples include polyamide particles.

[0125] There are no particular limitations on the inorganic filler used, and examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstenate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and carbon black. Silica is preferred. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica can be used as examples of silica.

[0126] Furthermore, the filler can be surface-treated as needed. There are no particular limitations on the surface treatment agent; examples include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Specific examples of surface treatment agents include 3-epoxypropoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

[0127] The filler can be used alone or in combination of two or more types.

[0128] The amount of filler used relative to 100 parts by weight of epoxy resin is preferably 0.5 parts by weight or more and 95 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less. From the perspective of fully imparting the effect of the filler, the amount of filler used is preferably 0.5 parts by weight or more. On the other hand, in order to avoid impairing moldability due to increased viscosity of the complex, the amount of filler used is preferably 95 parts by weight or less.

[0129] <Cured product>

[0130] This invention relates to cured products obtained by curing the resin composition. The active ester resin itself has a low dielectric loss tangent, therefore the cured product obtained from the resin composition containing the active ester resin also has a low dielectric loss tangent, which is a preferred method.

[0131] As a method for producing a cured product obtained by curing the resin composition of the present invention, for example, the heating temperature during heat curing is not particularly limited, but is preferably 100°C or higher and 300°C or lower, and the heating time is preferably 1 hour or higher and 24 hours or lower.

[0132] <Uses of Resin Compositions>

[0133] Examples of uses for the resin composition of the present invention include printed wiring board materials, resin compositions for flexible wiring substrates, interlayer insulating materials for add-on substrates, adhesive films for add-on substrates, insulating materials for circuit boards, resin casting materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, add-on films, add-on substrates, fiber-reinforced composite materials, and molded articles formed by curing the aforementioned composite materials. Among these various uses, in the applications of printed wiring board materials, insulating materials for circuit boards, and adhesive films for add-on substrates, it can be used as an insulating material for so-called electronic component embedded substrates where passive components such as capacitors and active components such as IC chips are embedded in the substrate. Furthermore, since the cured product has low dielectric properties, the resin composition of the present invention is preferably used in semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, flexible wiring substrates, add-on films, multilayer printed wiring boards, add-on substrates, fiber-reinforced composite materials, and molded articles formed by curing the aforementioned composite materials. Hereinafter, a method for manufacturing the semiconductor sealing materials, etc., from the resin composition will be described.

[0134] Semiconductor sealing materials

[0135] This invention relates to a semiconductor sealing material, characterized by containing the aforementioned resin composition. As a method for obtaining the semiconductor sealing material from the resin composition of this invention, methods include, as needed, using an extruder, kneader, roller, etc., to thoroughly melt and mix the resin composition of this invention, a curing accelerator, and an inorganic filler, etc., until homogeneous. In this case, fused silica is typically used as the inorganic filler; however, when used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, crystalline silica, alumina, silicon nitride, etc., which have higher thermal conductivity than fused silica, can be used. Regarding the filling ratio, it is preferable to use an inorganic filler in the range of 30 parts by weight or more and 95 parts by weight or less relative to 100 parts by weight of the resin composition; more preferably, it is 70 parts by weight or more, and even more preferably 80 parts by weight or more, to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the coefficient of linear expansion.

[0136] Semiconductor devices

[0137] This invention relates to a semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material. As a method for obtaining a semiconductor device from the resin composition of this invention, an example is to cast or mold the semiconductor sealing material using a transfer molding machine, injection molding machine, or the like, and then heat it at 50°C or higher and 200°C or lower for a period of 2 hours or more and 10 hours or less.

[0138] "Prepreg"

[0139] This invention relates to prepregs having a reinforcing substrate and a resin composition impregnated in the reinforcing substrate. A method for obtaining a prepreg from the resin composition of this invention includes impregnating a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving, etc.) with a resin composition that has been varnished with an organic solvent, and then heating it at a temperature corresponding to the type of solvent used, preferably 50°C or higher and 170°C or lower. The mass ratio of the resin composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferred that the resin content in the prepreg be 20% by mass or more and 60% by mass or less.

[0140] Examples of organic solvents used herein include methyl ethyl ketone, acetone, N,N-dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount used can be chosen according to the application. For example, in the case of further manufacturing printed circuit boards from prepreg as described below, polar solvents with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, and N,N-dimethylformamide, are preferred. In addition, it is preferable to use them at a ratio of 40% by mass or more and 80% by mass or less of non-volatile components.

[0141] Circuit board

[0142] This invention relates to a circuit board obtained by laminating the prepreg and copper foil and then heating and pressing them together. As a method for obtaining a printed circuit board from the resin composition of this invention, an example is to laminate the prepreg, appropriately overlap the copper foil, and heat and press it at a pressure of 1 MPa or more and 10 MPa or less, at a temperature of 170°C or more and 300°C or less for 10 minutes or more and 3 hours or less.

[0143] Flexible wiring substrate

[0144] As a method for manufacturing a flexible wiring substrate from the resin composition of the present invention, a method comprising the following three steps can be listed. The first step is to coat an electrically insulating film with a resin composition containing an active ester resin, an epoxy resin, and an organic solvent using a coating machine such as a reverse roller coating machine or a corner roller coating machine. The second step is to heat the electrically insulating film coated with the resin composition using a heating machine at a temperature of 60°C to 170°C for a period of 1 minute to 15 minutes, causing the solvent to evaporate from the electrically insulating film and thus B-stepping the resin composition. The third step is to heat-press a metal foil onto the B-stepped electrically insulating film of the resin composition using a heating roller or the like (preferably with a pressing pressure of 2 N / cm). 2 Above and 200 N / cm 2 The following steps involve applying an adhesive (with a pressing temperature of 40°C or higher and 200°C or lower). It should be noted that if sufficient adhesive performance can be achieved through the above three steps, the process can be terminated here. However, if complete adhesive performance is required, it is preferable to further perform post-curing at 100°C or higher and 200°C or lower for 1 hour or more and 24 hours. The thickness of the finally cured resin composition film is preferably in the range of 5 μm or more and 100 μm or less.

[0145] "Lamination membrane"

[0146] This invention relates to a build-up film containing the resin composition of the present invention. As a method for manufacturing the build-up film of the present invention, one example is a method of manufacturing an adhesive film for a multilayer printed circuit board by coating the resin composition of the present invention onto a support film to form a resin composition layer.

[0147] When manufacturing a laminated film from a resin composition, it is important that the film softens under the lamination temperature conditions (typically above 70°C and below 140°C) in a vacuum lamination process, and exhibits fluidity (resin flow) to fill the vias or holes present in the circuit board while being laminated to the circuit board. It is preferable to combine the above-mentioned components to exhibit such characteristics.

[0148] Here, the diameter of the through-holes in the multilayer printed wiring board is typically 0.1 mm or more and 0.5 mm or less, and the depth is typically 0.1 mm or more and 1.2 mm or less, preferably within this range, to be filled with resin. It should be noted that, in the case of both sides of the laminated circuit board, it is preferable to fill about 1 / 2 of the through-hole.

[0149] The adhesive film is manufactured as follows: After preparing a varnish-like resin composition, the varnish-like composition is coated onto the surface of a support film (Y), and then dried by heating or blowing hot air to form a composition layer (X) composed of the resin composition. The thickness of the formed composition layer (X) is generally preferably greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is generally in the range of 5 μm or more and 70 μm or less; therefore, the thickness of the resin composition layer is preferably 10 μm or more and 100 μm or less. It should be noted that the composition layer (X) in this invention can be protected by a protective film described later. By protecting it with a protective film, dust and other contaminants can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

[0150] The supporting film and protective film can be made of various materials, including polyethylene, polypropylene, polyvinyl chloride and other polyolefins, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate and other polyesters, polycarbonate, polyimide, and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that, in addition to matte treatment and corona treatment, the supporting film and protective film can also undergo a release treatment.

[0151] The thickness of the support film is not particularly limited, but is typically 10 μm or more and 150 μm or less, preferably in the range of 25 μm or more and 50 μm or less. Furthermore, the thickness of the protective film is preferably 1 μm or more and 40 μm or less.

[0152] The support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer through heat curing. Peeling off the support film (Y) after the adhesive film has been heat-cured prevents the adhesion of dust and other contaminants during the curing process. In the case of peeling after curing, the support film is typically pre-treated with a demolding process.

[0153] Multilayer printed wiring board

[0154] Multilayer printed wiring boards can be manufactured using the laminate film produced by the method described above. Regarding the manufacturing method of such a multilayer printed wiring board, for example, after peeling off the composite layers (X) which are protected by a protective film, the composite layers (X) are directly laminated onto one or both sides of the circuit board by, for example, vacuum lamination. The lamination method can be intermittent or continuous using rollers. Alternatively, the adhesive film and the circuit board can be heated (preheated) as needed before lamination. Regarding the lamination conditions, it is preferable to set the lamination temperature to 70°C or higher and 140°C or lower, and preferably to set the lamination pressure to 1 kgf / cm². 2 Above and 11 kgf / cm 2 Below (9.8×10 4 N / m 2 The above and 107.9×10 4 N / m 2 (The following) It is preferred to perform lamination under a reduced pressure of 20 mmHg (26.7 hPa) or less.

[0155] "Additional layer substrate"

[0156] As a method for manufacturing a build-up substrate using the resin composition of the present invention, a method comprising the following three steps can be listed. The first step involves applying a resin composition, appropriately incorporating rubber, fillers, etc., to a circuit board having circuits formed using a spraying method, curtain coating, or similar method, followed by curing. The second step involves subsequently creating predetermined through-holes, treating the surface with a roughening agent, washing it with hot water to create an uneven surface, and then plating it with a metal such as copper. The third step involves repeating this operation sequentially to alternately add layers of resin insulating layer and conductor layer with a predetermined circuit pattern. It should be noted that the through-holes are preferably created after the outermost resin insulating layer is formed. In addition to the solution coating method described above, the first step can also be performed by laminating a build-up film pre-coated to the desired thickness and dried. In addition, the additive substrate of the present invention can also be manufactured by heating and pressing a copper foil containing resin, which is formed by semi-curing the resin composition on a copper foil, at a temperature of 170°C or higher and 250°C or lower onto a wiring substrate on which circuits are formed, thereby omitting the steps of forming a roughened surface and plating treatment.

[0157] "Fiber-reinforced composite materials"

[0158] As a method for manufacturing fiber-reinforced composite materials from the resin composition of the present invention, a varnish can be prepared by uniformly mixing the components constituting the resin composition, then impregnating the varnish into a reinforcing substrate composed of reinforcing fibers and allowing it to cure. Specifically, the curing temperature is preferably in the range of 50°C to 250°C, and particularly preferably cured at 50°C to 100°C to form a non-sticky cured product, followed by further processing at a temperature of 120°C to 200°C. As reinforcing fibers, twisted yarn, untwisted yarn, or untwisted yarn can all be used. From the perspective of balancing the formability and mechanical strength of fiber-reinforced plastic components, untwisted yarn or untwisted yarn is preferred. Furthermore, the form of the reinforcing fibers can be a woven fabric with the fiber direction aligned in one direction. For the fabric, plain weave, satin weave, etc., can be freely selected depending on the application and purpose. Specifically, from the perspective of excellent mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc., can be listed, and two or more of them can be used together. From the viewpoint of improving the strength of the molded product, carbon fiber is preferred, and various types of carbon fiber, such as polyacrylonitrile-based, pitch-based, and rayon-based carbon fibers, can be used. Among these, polyacrylonitrile-based carbon fibers, which are readily available for obtaining high-strength carbon fibers, are preferred. When a varnish is impregnated into a reinforcing matrix composed of reinforcing fibers to produce a fiber-reinforced composite material, the amount of reinforcing fibers used is preferably an amount that results in a volume fraction of reinforcing fibers in the fiber-reinforced composite material that is 40% or more and 85% or less.

[0159] "Fiber-reinforced resin molded products"

[0160] As a method for manufacturing fiber-reinforced resin molded articles from the resin composition of the present invention, examples include methods such as curing a prepreg impregnated with varnish in a large autoclave, which is manufactured by: laying fiber aggregate on a mold and layering the varnish in multiple layers by hand lay-up or spraying; using either a male or female mold, layering and molding the varnish while impregnating a substrate formed of reinforcing fibers, covering with a flexible mold that allows pressure to be applied to the molded article, sealing it airtightly, and then vacuum (reduced pressure) molding; SMC pressing method, in which the varnish containing reinforcing fibers is pre-formed into sheets and then compressed and molded using a mold; and RTM method, in which the varnish is injected into a mold filled with fibers. The resulting fiber-reinforced resin molded article is a molded article having reinforcing fibers and a cured resin composition. Specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded article is preferably in the range of 40% by mass or more and 70% by mass or less, and from the perspective of strength, it is particularly preferably in the range of 50% by mass or more and 70% by mass or less.

[0161] The methods for manufacturing semiconductor sealing materials and the like have been described above, and other cured products can also be produced from the resin composition of the present invention. As a method for producing other cured products, it can be produced according to a general curing method for resin compositions. For example, the heating temperature conditions may be appropriately selected according to the type of the curing agent to be combined, the application, and the like.

[0162] Examples

[0163] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "% by mass". It should be noted that the GPC in the present examples, 13 CNMR, and MALDI-TOF-MS measurement conditions are as described below.

[0164] <GPC Measurement Conditions>

[0165] Measuring apparatus: "HLC-8320 GPC (registered trademark)" manufactured by Tosoh Corporation,

[0166] Column: Guard column "TSKgel (registered trademark) HXL-L" manufactured by Tosoh Corporation

[0167] + "TSKgel G4000 HXL" manufactured by Tosoh Corporation

[0168] + "TSKgel G3000 HXL" manufactured by Tosoh Corporation

[0169] + "TSKgel G2000 HXL" manufactured by Tosoh Corporation

[0170] + "TSKgel G2000 HXL" manufactured by Tosoh Corporation

[0171] Detector: RI (differential refractometer)

[0172] Data processing: "GPC Workstation EcoSEC (registered trademark) Workstation" manufactured by Tosoh Corporation

[0173] Measurement conditions: Column temperature 40°C

[0174] Developing solvent: Tetrahydrofuran

[0175] Flow rate: 1.0 mL / min

[0176] Standard sample: The following monodisperse polystyrene with known molecular weight is used according to the measurement manual of the GPC apparatus described above.

[0177] "A-500" manufactured by Tosoh Corporation

[0178] "A-1000" manufactured by Tosoh Corporation

[0179] "A-2500" manufactured by Tosoh Corporation

[0180] "A-5000" manufactured by Tosoh Corporation

[0181] "F-1" manufactured by Tosoh Corporation

[0182] "F-2" manufactured by Tosoh Corporation

[0183] "F-4" manufactured by Tosoh Corporation

[0184] "F-10" manufactured by Tosoh Corporation

[0185] "F-20" manufactured by Tosoh Corporation

[0186] "F-40" manufactured by Tosoh Corporation

[0187] "F-80" manufactured by Tosoh Corporation

[0188] "F-128" manufactured by Tosoh Corporation

[0189] Sample: 50 μL of a tetrahydrofuran solution (converted to 1.0% by mass based on resin solids content) obtained by filtering it through a microfilter.

[0190] (Example 1) Manufacturing of active ester resin (I-1)

[0191] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 183.3 g of α-naphthol, 494.1 g of methanediol (manufactured by Sumitomo Chemical Co., Ltd.), 474.2 g of toluene, and 3.4 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 5 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 1.5 g of 49% sodium hydroxide aqueous solution was added and stirred. The solvent was removed by vacuum distillation and the mixture was dried, thereby producing 550.0 g of phenolic hydroxyl-containing resin (A-1). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-1), determined by the neutralization titration method specified in JIS K0070 (1992), was 480 g / equivalent.

[0192] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.6 g of tetrabutylammonium bromide, 101.0 g of isophthaloyl chloride, 240.1 g of phenolic hydroxyl-containing resin (A-1), 72.1 g of α-naphthol, and 1130.2 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen, 206.0 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce a toluene solution of the active ester resin (I-1) (62% non-volatile components). The functional group equivalent of the active ester resin (I-1) is 377 g / equivalent, and the softening point is 146 °C as determined by JIS K7234.

[0193] (Example 2) Manufacturing of active ester resin (I-2)

[0194] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 225.0 g of α-naphthol, 357.8 g of methanediol (manufactured by Sumitomo Chemical Co., Ltd.), 407.9 g of toluene, and 2.9 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 8 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 1.3 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was then heated to reflux at 120°C for 1 hour to remove moisture, thereby producing 754.7 g of a toluene solution (64% non-volatile component) of the phenolic hydroxyl-containing resin (A-2). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-2), determined by neutralization titration according to JIS K0070 (1992), was 332 g / equivalent.

[0195] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 113.1 g of isophthaloyl chloride, 288.6 g of a toluene solution of phenolic hydroxyl-containing resin (A-2) (64% non-volatile component), 80.7 g of α-naphthol, and 1017.3 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 230.7 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 547.0 g of a toluene solution of the active ester resin (I-2) (63% non-volatile component). The functional group equivalent of the active ester resin (I-2) is 303 g / equivalent, and the softening point is 148℃ as determined by JIS K7234.

[0196] (Example 3) Manufacturing of active ester resin (I-3)

[0197] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 225.0 g of α-naphthol, 490.3 g of methanediol (manufactured by Sumitomo Chemical Co., Ltd.), 500.7 g of toluene, and 3.6 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 8 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 1.6 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was then heated to reflux at 120°C for 1 hour to remove moisture, thereby producing 958.5 g of a toluene solution (61% non-volatile component) of the phenolic hydroxyl-containing resin (A-3). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-3), determined by neutralization titration according to JIS K0070 (1992), was 401 g / equivalent.

[0198] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 90.9 g of isophthaloyl chloride, 391.4 g of a toluene solution of phenolic hydroxyl-containing resin (A-3) (61% non-volatile component), 43.3 g of α-naphthol, and 1025.7 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 185.4 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 523.5 g of a toluene solution of the active ester resin (I-3) (60% non-volatile component). The functional group equivalent of the active ester resin (I-3) is 380 g / equivalent, and the softening point is 171℃ as determined by JIS K7234.

[0199] (Example 4) Manufacturing of active ester resin (I-4)

[0200] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 225.0 g of β-naphthol, 606.4 g of methanediol (manufactured by Sumitomo Chemical Co., Ltd.), 582.0 g of toluene, and 4.2 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 8 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 1.8 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was then heated to reflux at 120°C for 1 hour to remove moisture, thereby producing 997.8 g of a toluene solution (46% non-volatile component) of the phenolic hydroxyl-containing resin (A-4). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-4), determined by neutralization titration according to JIS K0070 (1992), was 449 g / equivalent.

[0201] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 97.0 g of isophthaloyl chloride, 342.3 g of a toluene solution of phenolic hydroxyl-containing resin (A-4) (63% non-volatile component), 69.2 g of α-naphthol, and 1039.6 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 197.8 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 547.3 g of a toluene solution of the active ester resin (I-4) (64% non-volatile component). The functional group equivalent of the active ester resin (I-4) is 361 g / equivalent, and the softening point is 130℃ as determined by JIS K7234.

[0202] (Example 5) Manufacturing of active ester resin (I-5)

[0203] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 183.3 g of o-cresol, 658.7 g of methyl glycol (manufactured by Sumitomo Chemical Co., Ltd.), 842.0 g of toluene, and 2.5 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 22.7 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 6 hours to remove moisture. After cooling to 80°C, 11.0 g of 49% sodium hydroxide aqueous solution was added and stirred. After three separate washings with 421.0 g of water, the solvent was distilled off under reduced pressure and the mixture was dried, thereby producing 669.9 g of a phenolic hydroxyl-containing resin (A-5). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-5) determined by the neutralization titration method specified in JIS K0070 (1992) is 619 g / equivalent.

[0204] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 72.7 g of isophthaloyl chloride, 222.8 g of phenolic hydroxyl-containing resin (A-5), 51.9 g of α-naphthol, and 963.3 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen, 148.3 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 516.8 g of a toluene solution of the active ester resin (I-5) (59% non-volatile component). The functional group equivalent of the active ester resin (I-5) is 446 g / equivalent, and the softening point is 150 °C as determined by JIS K7234.

[0205] (Example 6) Manufacturing of active ester resin (I-6)

[0206] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 300.0 g of o-cresol, 652.1 g of methyl glycol (manufactured by Sumitomo Chemical Co., Ltd.), 666.5 g of toluene, and 3.2 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 15.8 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 8 hours to remove moisture. After cooling to 80°C, 8.3 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual o-cresol were removed by vacuum distillation, thereby producing 767.0 g of phenolic hydroxyl-containing resin (A-6). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-6), determined by the neutralization titration method specified in JIS K0070 (1992), was 415 g / equivalent.

[0207] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 105.0 g of isophthaloyl chloride, 215.6 g of phenolic hydroxyl-containing resin (A-6), 75.0 g of α-naphthol, and 1073.0 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen, 214.2 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce a toluene solution of the active ester resin (I-6) with 542.1 g of non-volatile components (58% non-volatile component). The functional group equivalent of the active ester resin (I-6) is 344 g / equivalent, and the softening point is 131℃ as determined by JIS K7234.

[0208] (Example 7) Manufacturing of active ester resin (I-7)

[0209] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 1200.0 g of 2,6-xylenol, 954.0 g of methylene glycol (manufactured by Sumitomo Chemical Co., Ltd.), 2154.0 g of toluene, and 6.5 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 58.2 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 8 hours to remove moisture. After cooling to 80°C, 28.3 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual 2,6-xylenol were removed by vacuum distillation, thereby producing 1672.7 g of a phenolic hydroxyl-containing resin (A-7). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-7) determined by the neutralization titration method specified in JIS K0070 (1992) is 252 g / equivalent.

[0210] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 105.0 g of isophthaloyl chloride, 130.9 g of phenolic hydroxyl-containing resin (A-7), 75.0 g of α-naphthol, and 819.0 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 214.2 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 440.6 g of a toluene solution of the active ester resin (I-7) (60% non-volatile component). The functional group equivalent of the active ester resin (I-7) is 262 g / equivalent, and the softening point is 129 °C as determined by JIS K7234.

[0211] (Example 8) Manufacturing of active ester resin (I-8)

[0212] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 225.0 g of phenol, 548.1 g of methylene glycol (manufactured by Sumitomo Chemical Co., Ltd.), 541.2 g of toluene, and 2.6 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 12.8 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 10 hours to remove moisture. After cooling to 80°C, 6.8 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual phenol were distilled off under reduced pressure, thereby producing 622.3 g of phenolic hydroxyl-containing resin (A-8). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-8), determined by the neutralization titration method specified in JIS K0070 (1992), was 344 g / equivalent.

[0213] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 117.2 g of isophthaloyl chloride, 199.4 g of phenolic hydroxyl-containing resin (A-8), 83.6 g of α-naphthol, and 1073.4 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 239.0 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 547.5 g of a toluene solution of the active ester resin (I-8) (62% non-volatile component). The functional group equivalent of the active ester resin (I-8) is 308 g / equivalent, and the softening point is 141℃ as determined by JIS K7234.

[0214] (Example 9) Manufacturing of active ester resin (I-9)

[0215] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 180.0 g of phenol, 594.5 g of methanediol (manufactured by Sumitomo Chemical Co., Ltd.), 542.2 g of toluene, and 2.6 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 12.8 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 10 hours to remove moisture. After cooling to 80°C, 6.8 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual phenol were distilled off under reduced pressure, thereby producing 618.2 g of phenol-hydroxyl-containing resin (A-9). The hydroxyl equivalent of the phenol-hydroxyl-containing resin (A-9), determined by the neutralization titration method specified in JIS K0070 (1992), was 433 g / equivalent.

[0216] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.5 g of tetrabutylammonium bromide, 103.4 g of isophthaloyl chloride, 221.8 g of phenolic hydroxyl-containing resin (A-9), 73.8 g of α-naphthol, and 1084.9 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen, 210.9 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 532.3 g of a toluene solution of the active ester resin (I-9) (65% non-volatile component). The functional group equivalent of the active ester resin (I-9) is 353 g / equivalent, and the softening point is 151 °C as determined by JIS K7234.

[0217] (Example 10) Manufacturing of active ester resin (I-10)

[0218] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 150.0 g of phenol, 619.3 g of methylene glycol (manufactured by Sumitomo Chemical Co., Ltd.), 538.5 g of xylene, and 2.6 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 150°C for 3 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 12.8 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 150°C for 13 hours to remove moisture. After cooling to 80°C, 6.7 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual phenol were distilled off under reduced pressure, thereby producing 621.5 g of phenol-hydroxyl-containing resin (A-10). The hydroxyl equivalent of the phenol-hydroxyl-containing resin (A-10), determined by the neutralization titration method specified in JIS K0070 (1992), was 640 g / equivalent.

[0219] In a reaction vessel equipped with a thermometer, dropping funnel, cooling pipe, fractionating pipe, and stirring device, 0.6 g of tetrabutylammonium bromide, 86.5 g of isophthaloyl chloride, 274.4 g of phenolic hydroxyl-containing resin (A-10), 61.8 g of α-naphthol, and 1174.4 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 179.9 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce 590.0 g of a toluene solution of the active ester resin (I-10) (59% non-volatile component). The functional group equivalent of the active ester resin (I-10) is 457 g / equivalent, and the softening point is 154 °C as determined by JIS K7234.

[0220] (Example 11) Manufacturing of active ester resin (I-11)

[0221] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 225.0 g of phenol, 548.1 g of methylene glycol (manufactured by Sumitomo Chemical Co., Ltd.), 541.2 g of toluene, and 2.6 g of p-toluenesulfonic acid monohydrate were added. The system was then purged with nitrogen under reduced pressure. The mixture was heated to reflux at 130°C for 2 hours while purging with nitrogen to remove moisture. After cooling to 80°C, 12.8 g of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux at 120°C for 13 hours to remove moisture. After cooling to 80°C, 6.8 g of 49% sodium hydroxide aqueous solution was added and stirred. The mixture was heated to 180°C, and the solvent and residual phenol were distilled off under reduced pressure, thereby producing 621.5 g of phenolic hydroxyl-containing resin (A-11). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (A-11), determined by the neutralization titration method specified in JIS K0070 (1992), was 341 g / equivalent.

[0222] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.4 g of tetrabutylammonium bromide, 12.9 g of isophthaloyl chloride, 101.6 g of benzoyl chloride, 289.8 g of phenolic hydroxyl-containing resin (A-11), and 814.8 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 178.5 g of a 20% sodium hydroxide aqueous solution was added dropwise over 1 hour with stirring, keeping the temperature of the reaction solution below 40°C. After the addition was complete, the mixture was heated and stirred at 40°C for 1 hour, and then heated and stirred at 60°C for 4 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce a toluene solution of the active ester resin (I-11) (57% non-volatile component). The functional group equivalent of the active ester resin (I-11) is 320 g / equivalent, and the softening point is 126 °C as determined by JIS K7234.

[0223] (Synthetic Reference Example 1) Preparation of Active Ester Resin (R-1)

[0224] In a reaction vessel equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirring device, 0.3 g of tetrabutylammonium bromide, 101.0 g of isophthaloyl chloride, 72.0 g of α-naphthol, 82.5 g of a dicyclopentadiene-phenol addition polymerization resin (hydroxyl equivalent: 165 g / equivalent, softening point 85℃), and 547.5 g of toluene were added. The system was then purged with nitrogen under reduced pressure. While purging with nitrogen, 206.0 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours with stirring, keeping the temperature of the reaction solution below 60℃. After the addition was complete, the mixture was heated and stirred at 60℃ for 3 hours. After neutralization with a 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure to produce a 65% toluene solution of the active ester resin (R-1). The functional group equivalent of the active ester resin (R-1) is 220 g / equivalent, and the softening point is 130 °C as determined by JIS K7234.

[0225] (Synthetic Reference Example 2) Preparation of Active Ester Resin (R-2)

[0226] In Reference Example 1, α-naphthol was changed to 48.0 g, the addition polymerization resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / equivalent, softening point 85 °C) was changed to 110.0 g, and toluene was changed to 556.3 g. Otherwise, a 65% toluene solution of the active ester resin (R-2) was prepared by the same method. The functional group equivalent of the active ester resin (R-2) was 224 g / equivalent, and the softening point, determined based on JIS K7234, was 150 °C.

[0227] Preparation of resin compositions (Examples 12 to 21, Comparative Examples 1 and 2)

[0228] The active ester resins (I-1) to (I-10) prepared in Examples 1 to 10 were distilled off to remove the solvent and then dried under vacuum at 180°C for 2 hours to obtain solid resin products. Using the obtained active ester resin solids, resin compositions were prepared by mixing the components in the mass ratios shown in Table 1 below. As the epoxy resin, bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC Corporation, epoxy equivalent 184~194 g / equivalent) was used. 4-Dimethylaminopyridine was used as the curing catalyst. Furthermore, as the active ester resin of Comparative Example 1, the active ester resin (R-1) prepared in Reference Example 1 was used; and as the active ester resin of Comparative Example 2, the active ester resin (R-2) prepared in Reference Example 2 was used.

[0229] [Table 1]

[0230]

[0231] (Examples 22 to 31, Comparative Examples 3 and 4) Preparation of resin cured products

[0232] The resin compositions prepared in Examples 12 to 21, and Comparative Examples 1 and 2 were poured into a mold (11 cm × 9 cm × 2.4 mm) and heated at 180°C and 0.5 MPa for 30 minutes using a press. The resulting molded articles were removed from the mold and cured at 175°C for 5 hours, thereby producing the resin cured articles shown in Table 2 below.

[0233] Determination of glass transition temperature

[0234] For the prepared resin cured products, the glass transition temperature was evaluated by using a viscoelasticity measuring device (SII NanoTechnology Co., Ltd. "DMS-6100") under the conditions of rectangular tensile method, frequency 1 Hz, and heating rate 3 °C / min, with the temperature at which the change in elastic modulus reached the maximum (the maximum tanδ change rate) as the glass transition temperature.

[0235] Determination of relative permittivity and dielectric loss tangent

[0236] In addition, for the prepared resin cured material, after vacuum drying at 105°C for 2 hours, and then storing it indoors at 23°C and 50% humidity for 24 hours, the relative permittivity and dielectric loss tangent at 1 GHz were measured. The measurements were performed using a network analyzer E8362C (manufactured by Agilent Technologies, Inc.) via the cavity resonance method. The results are shown in Table 2 below.

[0237] [Table 2]

[0238]

[0239] As shown in Table 2, it can be seen that the active ester resins (I-1) to (I-10) of the present invention have lower or the same dielectric loss tangent and lower relative dielectric constant compared with the active ester resin (R-1) of the comparative examples.

[0240] As shown in Examples 1 to 11, by varying the feed ratio of the phenolic hydroxyl-containing compound to the 1,3-diisopropenylbenzene precursor, resins (A-1) to (A-11) with various hydroxyl equivalents can be obtained. Furthermore, it is known that the reactive ester resins (I-1) to (I-11) of the present invention, manufactured using these resins, exhibit a wide range of functional group equivalents. On the other hand, as shown in Reference Examples 1 and 2, it is known that conventional reactive ester resins have a narrow range for adjusting functional group equivalents, resulting in significant variations in the resin's softening point.

[0241] The results above show that the functional group equivalent of the active ester resin of the present invention has a wide adjustment range, and the relative dielectric constant and dielectric loss tangent of the cured product are low.

Claims

1. An active ester resin obtained by reacting a phenolic hydroxyl-containing resin (A) with an aromatic (poly)carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl-containing resin (A) has a structure represented by the following formula (x). [Chemistry 1] In the formula, * indicates the bonding position. Ra represents a group selected from aliphatic hydrocarbon groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms, aryl groups with 3 to 20 carbon atoms, and aralkyl groups with 4 to 20 carbon atoms. When multiple Ra groups are present, they can be the same or different. k represents an integer from 0 to 3.

2. The active ester resin according to claim 1, wherein the resin (A) containing phenolic hydroxyl groups is represented by the following general formula (A1), [Chemistry 2] In the formula, A 1 and A 2 Each can independently represent a hydrocarbon ring or heterocycle with 3 to 18 carbon atoms that can be substituted. Ra represents a group selected from aliphatic hydrocarbon groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogen atoms, aryl groups with 3 to 20 carbon atoms, and aralkyl groups with 4 to 20 carbon atoms. When multiple Ra groups are present, they can be the same or different. k represents an integer from 0 to 3. n is the average number of repeating units, representing a value from 0.5 to 40.

3. The active ester resin according to claim 1 is obtained by reacting a phenolic hydroxyl-containing resin (A), an aromatic (poly)carboxylic acid or its acid halide (B), and a compound (C) that is different from the phenolic hydroxyl-containing resin (A) as a phenolic hydroxyl-containing compound.

4. A resin composition comprising the active ester resin according to any one of claims 1 to 3.

5. The resin composition according to claim 4, wherein it contains epoxy resin.

6. The resin composition according to claim 4, wherein it contains a phenolic resin and / or an active ester resin other than the active ester resin according to any one of claims 1 to 3.

7. A cured product obtained by curing the resin composition of claim 4.

8. A semiconductor sealing material, semiconductor device, prepreg, circuit board, flexible wiring board, extension film, multilayer printed wiring board, extension substrate, fiber-reinforced composite material, and a molded article formed by curing the fiber-reinforced composite material, all using the resin composition of claim 4.

9. A resin containing phenolic hydroxyl groups as described in claim 2, represented by general formula (A1).

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