Phenolic resin, epoxy resin, curable resin composition and cured product thereof

Abstract

The present invention relates to an epoxy resin represented by the following formula (1), wherein R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents an integer from 0 to 4. q represents an integer from 0 to 3. m and n represent the number of repetitions. The average value of m is m ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20. )

Description

Technical Field

[0001] The present invention relates to a phenol resin, an epoxy resin, a curable resin composition and a cured product thereof having a specific structure. Background Art

[0002] Phenolic resins and epoxy resins have excellent electrical properties (dielectric constant / dielectric tangent, insulation), mechanical properties, adhesion, thermal properties (heat resistance, etc.), etc., so they have been widely used in the electrical / electronic fields such as castings, laminated boards, IC sealing materials, structural materials, adhesives, coatings, etc.

[0003] Patent Document 1 describes an epoxy resin having a triglycidyl ether content of 40 to 75 area % and a tetraglycidyl ether content of 12 to 40 area % as measured by gel permeation chromatography.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2015-147854. Summary of the invention

[0007] [Problems to be solved by the invention]

[0008] In recent years, in the electrical / electronic field, it has been required to further improve the flame retardancy, moisture resistance, adhesion, dielectric properties, etc. of the resin composition, high purification, low viscosity for high filling of fillers (inorganic or organic fillers), various properties of reactivity improvement for shortening the molding cycle, etc. In addition, as a structural material, a lightweight and mechanically excellent material is required in aerospace materials, leisure / sports equipment uses, etc. In particular, in the field of semiconductor packaging, substrates (substrates themselves or their peripheral materials), according to the evolution of the semiconductor, thin-layer, stacking, systematization, three-dimensionalization become complicated, and have been required to have very high levels of heat resistance or high fluidity / low dielectric constant / low dielectric tangent.

[0009] Under such background, it is desired to develop a material that exhibits high heat resistance and has high fluidity, low dielectric constant, and low dielectric tangent.

[0010] The present invention has been made in view of the above problems, and an object of the present invention is to provide a phenol resin, an epoxy resin, and a curable resin composition containing the same, which have high fluidity and whose cured products have low dielectric constant and low dielectric tangent.

[0011] [Methods to solve the problem]

[0012] The present inventors have made intensive research to solve the above problems and finally completed the present invention. That is, the present invention relates to the following [1] to

[12] . In addition, in the present invention, "(numerical value 1) to (numerical value 2)" means including upper and lower limits. [1]

[0014] An epoxy resin represented by the following formula (1).

[0015]

[0016] (In formula (1), R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents an integer from 0 to 4. q represents an integer from 0 to 3. m and n represent the number of repetitions. The average value of m is m ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20. ) [2]

[0018] An epoxy resin represented by the following formula (2).

[0019]

[0020] (In formula (2), m and n are the number of repetitions, and the average value of m is m ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20. ) [3]

[0022] The epoxy resin as described in the above item [1] or [2] has a weight average molecular weight of 300 to 3000 as determined by gel permeation chromatography. [4]

[0024] A curable resin composition comprising the epoxy resin described in any one of [1] to [3] above. [5]

[0026] The curable resin composition as described in the above item [4] further contains a curing agent. [6]

[0028] A phenol resin represented by the following formula (3).

[0029]

[0030] (In formula (3), R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 4, and q represents a real number from 0 to 3. m and n are repeating numbers, and the average value of m is m aveSatisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20. ) [7]

[0032] A phenol resin represented by the following formula (4).

[0033]

[0034] (In formula (4), m and n are the number of repetitions, and 0<m<20, 1<n<20.) [8]

[0036] The phenol resin as described in the above item [6] or [7] has a weight average molecular weight of 250 to 3000 as determined by gel permeation chromatography. [9]

[0038] A curable resin composition comprising the phenol resin according to any one of the above items [6] to [8].

[10]

[0040] The curable resin composition as described in the above item [9] further contains an epoxy resin.

[11]

[0042] The curable resin composition as described in the above item [5] or

[10] further contains a curing accelerator.

[12]

[0044] A cured product obtained by curing the curable resin composition according to any one of the above items [4], [5], and [9] to

[11] .

[0045] [Effects of the invention]

[0046] The present invention relates to a phenol resin and an epoxy resin having high fluidity, and a cured product of a curable resin composition containing these has a low dielectric constant and a low dielectric tangent.

[0047] Therefore, the present invention can be used for insulating materials for electrical and electronic components (high reliability semiconductor packaging materials, etc.), laminates (printed wiring boards, build-up substrates, etc.), CFRP and other composite materials, adhesives, coatings, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 The GPC chart of Example 1 is shown.

[0049] Figure 2 The GC-MS spectrum of Example 1 is shown.

[0050] Figure 3 The GPC chart of Example 2 is shown.

[0051] Figure 4 The GPC chart of Example 5 is shown.

[0052] Figure 5 The GC-MS spectrum of Example 5 is shown. DETAILED DESCRIPTION

[0053] Hereinafter, the present invention will be described in detail.

[0054] 〔Epoxy resin〕

[0055] The epoxy resin of the present invention is represented by the following formula (1).

[0056]

[0057] (In formula (1), each of the plural Rs exists independently and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n are repeating numbers, and are 0<m<20, 1<n<20.)

[0058] The epoxy resin represented by the above formula (1) is designed as a molecule having polystyrene segments introduced therein, so as to have excellent high heat resistance, high fluidity, low dielectric constant, and low dielectric tangent.

[0059] The average value n of n in the above formula (1) is ave It can be calculated from the number average molecular weight obtained by gel permeation chromatography (GPC, detector: RI) or from the area ratio of each separated peak. ave 1<n ave <15 is more preferred, 1<n ave The average value m of m in the above formula (1) is particularly preferably ave It can be calculated from the number average molecular weight obtained by gel permeation chromatography (GPC, detector: RI) or from the area ratio of each separated peak. ave 0<m ave <15 is more preferred, and 0<m ave A value of <10 is particularly preferred.

[0060] The epoxy resin represented by the above formula (1) preferably has a weight average molecular weight of 300 to 3000, more preferably 350 to 2500, and even more preferably 400 to 2000, as measured by GPC. More preferably, the epoxy resin has a number average molecular weight of 200 to 3000, more preferably 250 to 2500, and even more preferably 300 to 2000, as measured by GPC.

[0061] When the weight average molecular weight and the number average molecular weight are less than the lower limit of the above range, it is difficult to obtain the heat resistance improvement effect obtained by increasing the molecular weight. In addition, when the weight average molecular weight and the number average molecular weight are greater than the upper limit of the above range, in addition to the difficulty of purification by washing with water, when used in semiconductor packaging materials, in addition to the viscosity being too high to ensure fluidity, and the difficulty of filling between wirings, in addition to the fluidity of the prepreg in substrate applications, it becomes difficult to ensure, and the embedding property of the wiring is impaired.

[0062] The epoxy resin represented by the above formula (1) is usually in a semi-solid to solid resin state at room temperature, and its softening point is preferably below 100°C, and more preferably below 90°C. When the softening point of the epoxy resin is higher than 100°C, the viscosity is high, and when the prepreg is made, the fiber impregnation will be reduced. In addition, the epoxy equivalent of the epoxy resin is preferably 200 to 1000 g / eq, more preferably 220 to 800 g / eq, particularly preferably 240 to 700 g / eq, and most preferably 250 to 600 g / eq. In addition, its melt viscosity (ICI viscosity) at 150°C is preferably 0.01 to 1.2 Pa·s, more preferably 0.01 to 1.0 Pa·s, and even more preferably 0.01 to 0.8 Pa·s. If it is within the above range, when it is used as a packaging material composition, suitable fluidity as a packaging material can be ensured.

[0063] Here, the melt viscosity (ICI viscosity) can be measured by a cone-plate viscometer (ICI viscometer) described in JIS K5600-2-3.

[0064] In the above formula (1), hydrogen is more preferably present as plural R. That is, an example of a more preferred structure of the epoxy resin represented by the above formula (1) is an epoxy resin represented by the following formula (2).

[0065]

[0066] (In formula (2), m and n are the number of repetitions, and the average value of m is m ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20. )

[0067] The preferred ranges of m and n in the above formula (2) are as follows: ave and the average value of n ave The more preferred range of is the same as that of the aforementioned formula (1).

[0068] The epoxy resin represented by the above formula (2) has low crystallinity and good solvent solubility, so the risk of crystallization in the solvent can be reduced.

[0069] 〔Phenolic resin〕

[0070] The manufacturing method of the epoxy resin of the present invention is not particularly limited, but for example, the epoxy resin can be obtained by using the phenol resin represented by the following formula (3) as a raw material. Specifically, the epoxy resin represented by the following formula (3) can be obtained by subjecting the phenol resin to addition or ring-closure reaction with epihalohydrin in the presence of a solvent and a catalyst. The amount of epihalohydrin used is generally 1.0 to 20.0 mol, preferably 1.5 to 10.0 mol, relative to 1 mol of phenolic hydroxyl groups of the phenol resin.

[0071]

[0072] (In formula (3), the plural Rs are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p represents a real number from 0 to 5, q represents a real number from 0 to 4, m and n represent repeating numbers, and 0<m<20, 1<n<20.)

[0073] The preferred ranges of R, p, q, m, and n in the above formula (3) and the average value of m are ave and the average value of n ave The more preferred range of is the same as that of the aforementioned formula (1).

[0074] The phenol resin represented by the above formula (3) preferably has a weight average molecular weight of 200 to 4500, more preferably 250 to 4000, and even more preferably 250 to 3000 as measured by GPC. The number average molecular weight is preferably 150 to 4500, more preferably 200 to 4000, and even more preferably 200 to 3000. The hydroxyl equivalent is preferably in the range of 100 to 500 g / eq., more preferably 120 to 400 g / eq., and even more preferably 120 to 300 g / eq.

[0075] The melt viscosity at 150° C. (ICI viscosity) is preferably in the range of 0.01 to 3.0 Pa·s, more preferably 0.02 to 2.0 Pa·s, and even more preferably 0.02 to 1.5 Pa·s.

[0076] The softening point is preferably in the range of 40 to 180°C, more preferably 40 to 150°C, and even more preferably 40 to 140°C. When the softening point is less than 40°C, it is difficult to obtain the heat resistance improvement effect due to the increase in molecular weight. In addition, when the softening point is higher than 180°C, in addition to the difficulty in purification by water washing, etc., when used as a hardener for semiconductor packaging materials, etc., or when used as an epoxy, in addition to the viscosity being too high and the inability to ensure fluidity, it is difficult to focus on the wiring, and it is difficult to ensure the fluidity of the prepreg in the substrate application, and the embedding property of the wiring is impaired.

[0077] Alkali metal hydroxides that can be used in the epoxidation reaction include sodium hydroxide, potassium hydroxide, etc. Alkali metal hydroxides can be solid components, and their aqueous solutions can also be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide can be continuously added to the reaction system, and water and epihalohydrin can be continuously distilled off under reduced pressure or normal pressure, and then liquid separation is performed to remove water, and epihalohydrin is continuously returned to the reaction system. Relative to 1 mole of phenolic hydroxyl groups of phenolic resin, the usage amount of alkali metal hydroxide is generally 0.9 to 2.5 moles, and more preferably 0.95 to 1.5 moles. If the usage amount of alkali metal hydroxide is small, the reaction will not be fully carried out. On the other hand, the excessive use of alkali metal hydroxides exceeding 2.5 moles relative to 1 mole of phenolic hydroxyl groups of phenolic resin will lead to the by-generation of unnecessary waste.

[0078] In order to promote the above-mentioned reaction, the quaternary ammonium salt of tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride etc. can be added as catalyst. Relative to 1 mole of phenolic hydroxyl group of phenolic resin, the usage amount as quaternary ammonium salt is generally 0.1 to 15g, more preferably 0.2 to 10g. If the usage amount is too little, can't obtain sufficient reaction promotion effect, if the usage amount is too much, the quaternary ammonium salt amount remaining in the epoxy resin will increase, so also can become the reason that makes electrical reliability variation.

[0079] During the epoxidation reaction, it is preferred to add alcohols such as methanol, ethanol, isopropanol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane and other aprotic polar solvents to react. When alcohols are used, the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight relative to the amount of epihalohydrin. In addition, when aprotic polar solvents are used, the amount used is usually 5 to 100% by weight, preferably 10 to 80% by weight, relative to the amount of epihalohydrin. The reaction temperature is usually 30 to 90°C, preferably 35 to 80°C. The reaction time is usually 0.5 to 100 hours, preferably 1 to 30 hours.

[0080] After the reaction is terminated, the reactant is washed with water, or the epihalohydrin or solvent is removed under heating and reduced pressure without washing. In addition, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin can also be dissolved in a solvent such as toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react to confirm the ring closure. At this time, the amount of alkali metal hydroxide used is generally 0.01 to 0.3 moles, preferably 0.05 to 0.2 moles, relative to 1 mole of phenolic hydroxyl groups of the phenol resin used for glycidylation. The reaction temperature is generally 50 to 120°C, and the reaction time is generally 0.5 to 24 hours. After the reaction is terminated, the generated salt is removed by filtration, washing with water, etc., and the epoxy resin of the present invention can be obtained by further distilling off the solvent under heating and reduced pressure.

[0081] Here, the method for producing the phenol resin shown in the above formula (3) is described. The method for producing the phenol resin shown in the above formula (3) is not particularly limited, but can be obtained by reacting an aromatic vinyl compound and an aromatic aldehyde in the presence of a protonic acid catalyst to obtain a reactant, and then further reacting phenols. More specifically, after a styrene compound and a benzaldehyde compound are subjected to a Prins reaction in the presence of an acid catalyst such as sulfonic acid, a phenol compound is added, and the reaction is obtained by heating / reacting the phenol compound again. At this time, as a substituent of the phenol compound, it is more preferred to have an alkyl group with no substitution or a carbon number of 1 to 5. From the perspective of improving heat resistance, it is more preferred to have an alkyl group with no substitution or a carbon number of 1 to 3. When synthesizing, in terms of an acid catalyst, in addition to using hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, solid acids such as silica alumina, and acidic ion exchange resins can also be used. These can be used alone or in combination with two or more. Relative to the sum of the weight of the styrene-based compounds and benzaldehyde-based compounds belonging to the reaction matrix, the amount of the catalyst used is 0.01 to 10 weight %, more preferably 0.1 to 5 weight %. If the amount of the catalyst used is too much, there is a worry that useless waste increases, and if it is too little, there is a worry that the reaction is slowed down. As the solvent used, for example, non-water-soluble solvents such as aromatic solvents of toluene, xylene, aliphatic solvents of cyclohexane, normal hexane, ethers of diethyl ether, diisopropyl ether, ester solvents of ethyl acetate, butyl acetate, methyl isobutyl ketone, cyclopentanone, etc. can be listed, but it is not limited to these, and more than two kinds can also be used in combination. In addition, in addition to the aforementioned non-water-soluble solvent, a non-protonic polar solvent can also be used in combination. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone (Methyl pyrrolidone), etc. can be listed, and two or more kinds can also be used in combination. When using a non-protonic polar solvent, it is more preferred to use a non-water-soluble solvent with a boiling point higher than that used in combination. The reaction temperature is preferably 80 to 180°C, more preferably 90 to 160°C, and even more preferably 100°C to 140°C. If the reaction temperature is too high, there is a concern that the Prince reaction product (in this specification, a substance that reacts a styrene compound and a benzaldehyde compound with an acid catalyst) will volatilize, and if the reaction temperature is too low, there is a concern that the reaction will not proceed fully. When the Prince reaction product reacts with a phenolic compound, water is produced as a by-product, so when the temperature is raised, it is removed from the system while azeotropically co-existing with the solvent. After the reaction is terminated, the acidic catalyst is neutralized with an alkaline aqueous solution, a water-insoluble organic solvent is added to the oil layer, and water washing is repeated until the wastewater becomes neutral, and then the solvent is removed under heating and reduced pressure. When activated clay or ion exchange resin is used, after the reaction is terminated, the reaction solution is filtered to remove the catalyst.

[0082] In the above formula (3), hydrogen is more preferably present as plural R. That is, an example of a more preferred structure of the phenol resin represented by the above formula (3) is a phenol resin represented by the following formula (4).

[0083]

[0084] (In formula (4), m and n are the number of repetitions, and the average value of m is m ave Satisfy 0<m ave <20, and the average value of n ave Satisfy 1<n ave <20. )

[0085] The more preferred ranges of m and n in the above formula (4), and the average value of m are ave and the average value of n ave The more preferred range of is the same as that of the aforementioned formula (3).

[0086] Hereinafter, the curable resin composition according to the present invention will be described.

[0087] The curable resin composition of the present invention contains the epoxy resin of the present invention or the phenol resin of the present invention as an essential component.

[0088] [Curing resin composition containing epoxy resin]

[0089] The curable resin composition containing epoxy resin of the present invention can use the epoxy resin of the present invention alone or in combination with other epoxy resins. When the epoxy resin of the present invention is used in combination with other epoxy resins, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 10 to 98% by weight, more preferably 20 to 95% by weight, and even more preferably 30 to 95% by weight. By setting the addition amount of the epoxy resin of the present invention to 10% by weight or more, the dielectric constant and dielectric tangent can be reduced, and high heat resistance and high fluidity can be exhibited.

[0090] Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present embodiment include condensation products of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzenes, alkyl-substituted dihydroxybenzenes, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polymers of the aforementioned phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbatadiene, vinyl norbatadiene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polymers of the aforementioned phenols and Condensation products of ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); Condensation products of the aforementioned phenols and aromatic dimethanols (benzenedimethanol, biphenyl dimethanol, etc.); Condensation products of the aforementioned phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.); Condensation products of the aforementioned phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethyl biphenyl, bisphenoxymethyl biphenyl, etc.); Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc., obtained by glycidylating the condensation products of the aforementioned bisphenols and various aldehydes or alcohols, etc., but generally, any epoxy resin that can be used is not limited to these. These can be used alone or in combination of two or more.

[0091] The curing agent that can be used in the curable resin composition containing epoxy resin of the present embodiment includes amine curing agents, acid anhydride curing agents, amide curing agents, phenol curing agents, etc. Specific examples of curing agents that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and the like. -Diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 4,4'-methylenebis(N-methylaniline), bis(aminophenyl)fluorene, 3,4'-diaminodiphenyl ether, 4,4'-diamino Diphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 1,3'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)biphenyl, 4,4'-(1,3-phenylenediisopropylidene)diphenylamine, 4,4'-(1,4-phenylenediisopropylidene)diphenylamine, naphthalene diamine, benzidine, dimethylbenzidine, internationally known Aromatic amine compounds such as aromatic amine compounds described in Synthesis Example 1 and Synthesis Example 2 of Publication No. 2017 / 170551, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine, 4,4'-methylenebis(cyclohexylamine), norbatane diamine, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, dimer diamine, triethylenetetramine and other aliphatic amines, but not limited thereto, can be used appropriately according to the characteristics to be imparted to the composition. In order to ensure the operation time, it is more preferred to use aromatic amines, that is, when curing properties are to be imparted, it is more preferred to use aliphatic amines. By using an amine compound containing a bifunctional component as the main component as a curing agent, a highly linear network can be constructed during the curing reaction, and particularly excellent toughness can be exhibited.In addition, amide compounds such as polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine; anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalic aldehyde, crotonaldehyde, myristic aldehyde, etc.); polycondensates of the above phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, isoflurane, etc.); The present invention also includes phenolic compounds such as polymers of phenols (such as butadiene, vinyl norbornane, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or condensation products of the aforementioned phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), or condensation products of the aforementioned phenols and aromatic dimethanols (benzenedimethanol, biphenyl dimethanol, etc.), or condensation products of the aforementioned phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), or condensation products of the aforementioned phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or condensation products of the aforementioned bisphenols and various aldehydes, and modified products thereof; imidazole, trifluoroborane-amine complex, guanidine derivatives, etc., but are not limited to these. In addition, a phenol resin represented by the above formula (3) or a phenol resin represented by the above formula (4) may be used as a hardener.

[0092] [Curing resin composition containing phenol resin]

[0093] The curable resin composition containing the phenol resin of the present embodiment may use the phenol resin of the present embodiment alone or in combination with other phenol resins or other curing agents.

[0094] When the phenol resin of the present embodiment is used together with other phenol resins or hardeners other than phenol resins, the proportion of the phenol resin of the present embodiment in the total amount of all phenol resins and hardeners other than phenol resins is preferably 10 to 98 wt %, more preferably 20 to 95 wt %, and even more preferably 30 to 95 wt %. By setting the addition amount of the phenol resin of the present embodiment to 10 wt % or more, the dielectric constant and dielectric tangent can be reduced, and the characteristics can be improved or low water absorption and high fluidity can be exhibited.

[0095] Specific examples of other phenolic resins that can be used in combination with the phenolic resin of the present embodiment include condensation products of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, myristic aldehyde, etc.); condensation products of the aforementioned phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbatadiene, vinyl norbatadiene, tetrahydroindene, etc.); , divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polycondensates of the aforementioned phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of the aforementioned phenols and aromatic dimethanols (benzenedimethanol, biphenyl dimethanol, etc.); polycondensates of the aforementioned phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of the aforementioned phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), etc., but not limited to these. These may be used alone or in combination of two or more.

[0096] In the curable resin composition containing the phenol resin of the present embodiment, the curing agent that can be used together with the phenol resin of the present embodiment (excluding the other phenol resins mentioned above) can include amine curing agents, acid anhydride curing agents, amide curing agents, phenol curing agents, etc. Specific examples of curing agents that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and the like. -Diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 4,4'-methylenebis(N-methylaniline), bis(aminophenyl)fluorene, 3,4'-diaminodiphenyl ether, 4,4'-diamino 1,3'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)biphenyl, 4,4'-(1,3-phenylenediisopropylidene)diphenylamine, 4,4'-(1,4-phenylenediisopropylidene)diphenylamine, naphthalene diamine, benzidine, dimethylbenzidine, international Aromatic amine compounds such as aromatic amine compounds described in Synthesis Example 1 and Synthesis Example 2 of Publication No. 2017 / 170551, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine, 4,4'-methylenebis(cyclohexylamine), norbatane diamine, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, dimer diamine, triethylenetetramine and other aliphatic amines, but not limited thereto, can be used appropriately according to the characteristics to be imparted to the composition. In order to ensure the operation time, it is more preferred to use aromatic amines, that is, when curing properties are to be imparted, it is more preferred to use aliphatic amines. By using an amine compound containing a bifunctional component as the main component as a curing agent, a highly linear network can be constructed during the curing reaction, and particularly excellent toughness can be exhibited. In addition, examples include amide compounds such as polyamide resins synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine; anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; imidazole, trifluoroborane-amine complex, guanidine derivatives, etc., but are not limited to these.

[0097] The curable resin composition containing a phenol resin according to the present embodiment may contain an epoxy resin. Specific examples of epoxy resins other than the epoxy resin represented by formula (1) include condensation products of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, myristic aldehyde, etc.); polymers of the aforementioned phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbatadiene, vinylnorbatadiene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polymers of the aforementioned phenols and ketones Condensation products of phenols (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylbenzene, benzophenone, etc.); Condensation products of the aforementioned phenols and aromatic dimethanols (benzenedimethanol, biphenyl dimethanol, etc.); Condensation products of the aforementioned phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.); Condensation products of the aforementioned phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethyl biphenyl, bisphenoxymethyl biphenyl, etc.); Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc., which are obtained by glycidylating the condensation products of the aforementioned bisphenols and various aldehydes or alcohols, but there is no limitation to these as long as they are commonly used epoxy resins. These may be used alone or in combination of two or more. In addition, the epoxy resins represented by the aforementioned formula (1) and the epoxy resins represented by the aforementioned formula (2) may also be used.

[0098] In the curable resin composition containing epoxy resin of the present embodiment, the total amount of curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of epoxy group of the epoxy resin. By setting the amount to 0.5 to 1.5 equivalents, good curing properties can be obtained.

[0099] The curable resin composition of this embodiment may be used in combination with the above-mentioned curing agent and a curing accelerator. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, and 1,8-diazabicyclo(5,4,0)-7-undecene, and phosphines such as triphenylphosphine, tri(tolyl)phosphine, tetraphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate. Phosphonium compounds, organic phosphines such as tributylphosphine, metal compounds such as tin octanoate, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, salicylic acid, etc. Carboxylic acid compounds such as salicylic acid are more preferred from the viewpoint of promoting the curing reaction of the amine compound and the epoxy resin. The curing accelerator can be used in an amount of 0.01 to 15 parts by weight relative to 100 parts by weight of the epoxy resin as needed.

[0100] In addition, in the curable resin composition of the present embodiment, an inorganic filler may be added as needed. Examples of inorganic fillers include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, spinel, titanium oxide, talc, etc., or beads obtained by spheronization of these, but are not limited to these. These may be used alone or in combination of two or more. The amount of these inorganic fillers used varies depending on the application, but when used, for example, in the case of encapsulants for semiconductors, it is preferred to use a proportion of 20% by weight or more in the curable resin composition in terms of heat resistance, moisture resistance, mechanical properties, flame resistance, etc. of the cured product of the curable resin composition, more preferably 30% by weight or more, and in particular, in order to increase the linear expansion coefficient with the lead frame, it is more preferred to use a proportion of 70 to 95% by weight.

[0101] In order to make the release from the mold during molding good, the curable resin composition of this embodiment can be formulated with a release agent. As the release agent, any of the previously publicly known ones can be used, but for example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid and their metal salts, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. can be listed. These can be used alone or in combination of two or more. The mixing amount of these release agents is preferably 0.5 to 3 weight % relative to the total organic components. If it is too less than this, the release from the mold will be poor, and if it is too much, the adhesion with the lead frame, etc. will be poor.

[0102] In order to improve the adhesion between the inorganic filler and the resin component, the curable resin composition of the present embodiment can adjust the coupling agent. As a coupling agent, any of the previously publicly known ones can also be used, but for example, various alkoxysilane compounds, alkoxytitanium compounds, aluminum chelating agents such as vinyl alkoxysilane, epoxy alkoxysilane, styryl alkoxysilane, methacryloxy alkoxysilane, acryloxy alkoxysilane, amino alkoxysilane, thioalkoxysilane, isocyanate alkoxysilane, etc. can be listed. These can be used alone or in combination of two or more. The method of adding the coupling agent is to pre-treat the surface of the inorganic filler with the coupling agent, and then mix it with the resin, or to mix the coupling agent in the resin and then mix the inorganic filler.

[0103] In addition, the curable resin composition of the present embodiment may be formulated with publicly known additives as needed. Specific examples of usable additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether compounds, resins containing active olefins, isocyanate resins, polyamide resins, polystyrene, polyethylene, polyimide resins, fluororesins, maleimide compounds, cyanate resins, active ester resins, silicone gels, silicone oils, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. Specific examples of more preferred compounds are listed below, but are not limited to these.

[0104] 〔Polyphenylene ether compounds〕

[0105] As the polyphenylene ether compound, any publicly known one can be used, but from the viewpoint of heat resistance and electrical properties, a polyphenylene ether compound having an ethylenically unsaturated double bond is more preferred, and a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure is more preferred. Commercially available products include SA-9000-111 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) or OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure).

[0106] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product may not be sufficient. In addition, if the molecular weight is greater than 5000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, so there is a tendency to become poorly formed. In addition, the reactivity is also reduced, and the curing reaction takes a long time, and the unreacted substances that are not taken in by the curing system will increase, and there is a tendency for the glass transition temperature of the cured product to decrease, and the heat resistance of the cured product to decrease.

[0107] When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it can maintain excellent dielectric properties and exhibit excellent heat resistance and moldability, etc. The number average molecular weight here can be specifically measured by gel permeation chromatography or the like.

[0108] The polyphenylene ether compound can be obtained by polymerization reaction, or by making the high molecular weight polyphenylene ether compound with a number average molecular weight of about 10000 to 30000 obtained by polymerization reaction and phenolic compounds undergo redistribution reaction to obtain. In addition, these can be used as raw materials, and can be reacted by making compounds with ethylenic unsaturated double bonds such as methacryloyl chloride, acryloyl chloride, chloromethyl styrene, etc. to impart free radical polymerizability. The polyphenylene ether compound obtained by the redistribution reaction can, for example, be obtained by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene and in the presence of a phenolic compound and a free radical initiator and undergoing redistribution reaction. In this way, the polyphenylene ether compound obtained by the redistribution reaction, because it has a hydroxyl group derived from a phenolic compound that contributes to hardening at both ends of the molecular chain, can maintain higher heat resistance, and is more preferably in terms of the point that functional groups can be introduced at both ends of the molecular chain after modification with a compound with ethylenic unsaturated double bonds. In addition, from the point of showing excellent fluidity, the polyphenylene ether compound obtained by the polymerization reaction is more preferably.

[0109] The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc., in the case of a polyphenylene ether compound obtained by a polymerization reaction. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is believed that the amount of the phenolic compound used in the redistribution reaction is adjusted. That is, the more the amount of the phenolic compound is, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound subjected to the redistribution reaction. In addition, the phenolic compound used in the aforementioned redistribution reaction is not particularly limited, but for example, it is more preferred to use a multifunctional phenolic compound having more than two phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc. These can be used alone or in combination of two or more.

[0110] The content of the polyphenylene ether compound is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, relative to the total mass of the curable resin component. If the content of the polyphenylene ether compound is 10 to 90% by mass, it is more preferred because a cured product having excellent heat resistance and the like can be obtained while fully utilizing the excellent dielectric properties of the polyphenylene ether compound.

[0111] [Reactive olefin-containing resin]

[0112] Condensation products of the aforementioned phenol resins and halogen compounds containing active olefins (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), polycondensates of phenols containing active olefins (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4 , 4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, chlorinated cyanuric acid, etc.), condensation products of epoxy resins or alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimide) bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene), ZYROCK maleimide resin (ANILIX maleimide, manufactured by Mitsui Chemicals FINE Co., Ltd.), biphenyl aralkyl type maleimide resin (the resin solution containing maleimide resin (M2) described in Example 4 of Japanese Patent Publication No. 2009-001783 is distilled under reduced pressure to remove the solvent and solidify it), diamino isopropylphenyl type maleimide (maleimide resin described in International Publication No. 2020 / 054601).

[0113] 〔Isocyanate resin〕

[0114] Aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbatene diisocyanate, and lysine diisocyanate; polyisocyanates such as biuret forms of one or more isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; polyisocyanates obtained by amination reaction of the above isocyanate compounds with polyol compounds.

[0115] 〔Polyamide resin〕

[0116] The polyamide resin is a polymer having one or more selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.) and lactams (ε-caprolactam, ω-undecanealactam, ω-laurolactam) as main raw materials; a polymer having one or more diamines and one or more dicarboxylic acids as main raw materials; or a polymer having amino acids, lactams, diamines and dicarboxylic acids as main raw materials. Examples of diamines include aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane; alicyclic diamines such as cyclohexanediamine, bis-(4-aminocyclohexyl)methane, and bis(3-methyl-4-aminocyclohexyl)methane; and aromatic diamines such as xylenediamine. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and dialkyl esters and dichlorides of these dicarboxylic acids.

[0117] 〔Polyimide resin〕

[0118] The polyimide resin is a polycondensate of the aforementioned diamine and tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic anhydride, 1,1-ethylene-4,4'-diphthalic anhydride, 2,2'-propylene-4,4'-diphthalic anhydride, 1,2 -vinyl-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 4,4'-oxydiphthalic anhydride, sulfur-4,4'-diphthalic anhydride, sulfonyl-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3 ,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride dianhydride, vinyl tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,2-vinyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxygen-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfur-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2 ,1] octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride. ,

[0119] 〔Cyanate ester resin〕

[0120] Cyanate resin is a cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)sulfide, phenol novolac cyanate group, and the like obtained by converting the hydroxyl group of phenol / dicyclopentadiene co-condensate into a cyanate group, but are not limited to these.

[0121] In addition, cyanate ester compounds whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferred because of their low hygroscopicity, flame resistance, and excellent dielectric properties.

[0122] Cyanate ester resins can be used to trimerize cyanate groups to form symmetrical trimeric Since the curable resin composition contains sym-triazine ring, it may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylate, dibutyltin maleate, etc. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the curable resin composition.

[0123] 〔Active ester resin〕

[0124] The active ester resin is a compound having one or more active ester groups in one molecule. As for the hardener of the curable resin composition of the present embodiment, an active ester resin can be used as needed. The active ester resin (active ester hardener) used as a hardener is preferably a compound having two or more ester groups with high reactivity such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds in one molecule. The active ester hardener is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound, and at least one of a hydroxyl compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxyl compound is more preferred, and an active ester hardener obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound is more preferred.

[0125] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0126] Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglycine, benzenetriol, dicyclopentadiene-type diphenolic compounds, and phenol novolacs. Here, the term "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

[0127] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene diphenol structure are more preferred. The so-called "dicyclopentadiene diphenol structure" means a divalent structural unit composed of a phenylene-dicyclopentylene-phenylene group.

[0128] Commercially available products of active ester-based hardeners include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) for active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" (manufactured by DIC Corporation) for active ester compounds containing a naphthalene structure; and "EXB9417-70BK" (manufactured by DIC Corporation) for active ester compounds containing a phenolic structure. As for the active ester compound of the acetylated product of the varnish, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be listed; as for the active ester compound of the benzoylated product containing phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) can be listed; as for the active ester hardener belonging to the acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be listed; as for the active ester hardener containing a phosphorus atom, "EXB-9050L-62M" manufactured by DIC Corporation can be listed; etc.

[0129] The curable resin composition of this embodiment may also be used in combination with a curing accelerator (curing catalyst) to improve the curability. Specific examples of curing accelerators that can be used include olefin compounds or maleimide compounds, etc., for the purpose of promoting the self-polymerization of the curable resin that can be free radical polymerized or the free radical polymerization of other components, and it is more preferable to use a free radical polymerization initiator. Examples of the free radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, diisopropyl peroxide, dialkyl peroxides such as 1,3-bis-(tert-butylperoxyisopropyl)-benzene, tert-butyl peroxybenzoate, peroxyketals such as 1,1-di-tert-butylperoxycyclohexane, α-isopropyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylol The curing accelerators include alkyl peresters such as methyl hexanoate, tert-butyl peroxy-3,5,5-trimethyl hexanoate, and tert-amyl peroxybenzoate, peroxy carbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane, organic peroxides such as tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl peroxyoctanoate, and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile, 4,4'-azobis(4-cyanoethyl oxalic acid), and 2,2'-azobis(2,4-dimethylvaleronitrile), but are not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are more preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is too large, the molecular weight will not be sufficiently extended during the polymerization reaction.

[0130] The curable resin composition of the present embodiment can be obtained by uniformly mixing the above-mentioned components. The curable resin composition of the present embodiment can be easily formed into a cured product by the same method as the conventionally known method. For example, the epoxy resin and the curing agent, and the curing accelerator, the inorganic filler, the release agent, the silane coupling agent and the additives as needed are fully mixed using an extruder, a kneader, a roller, etc. until they become uniform, so as to obtain the curable resin composition of the present embodiment, and this is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, etc., and further heated at 80 to 200° C. for 2 to 10 hours to obtain a cured product.

[0131] In addition, the curable resin composition of the present embodiment may contain a solvent as needed. The curable resin composition (varnish) containing a solvent is a prepreg impregnated in a fibrous material (substrate) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heated and dried to form a cured product of the curable resin composition of the present embodiment. The solvent content of the curable resin composition is generally 10 to 70% by weight, preferably about 15 to 70% by weight, as calculated by the internal content ratio. As the solvent, for example, amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone can be listed; sulfones such as tetramethylene sulfone; ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether are preferably mono- or di-lower (carbon number 1 to 3) alkyl ethers of lower (carbon number 1 to 3) alkanediols; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferably two alkyl groups that are the same or different. Di-lower (carbon number 1 to 3) alkyl ketones; aromatic solvents such as toluene and xylene can be listed. These can be used alone or as a mixed solvent of two or more.

[0132] Alternatively, the epoxy resin varnish is applied to a release film and the solvent is removed by heating to B-stage the film, thereby obtaining a sheet-like adhesive (also simply referred to as a sheet). The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

[0133] The hardened material obtained in this embodiment can be used for various purposes. Specifically, general uses of thermosetting resins such as epoxy resins can be listed, such as adhesives, coatings, coating agents, forming materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), encapsulants, and additives to other resins can also be listed.

[0134] As adhesives, adhesives for civil engineering, construction, automobiles, general offices, and medical use can be listed, as well as adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, semiconductor adhesives such as die-bonding agents and bottom fillers, bottom fillers for BGA reinforcement, and packaging adhesives such as anisotropic conductive films (ACFs) and anisotropic conductive pastes (ACPs).

[0135] Examples of encapsulants include bonding, dipping, and transfer molding mold packaging for capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs, bonding packaging for COB, COF, and TAB of ICs and LSIs, bottom fillers for flip chips, and packaging for IC packages such as QFP, BGA, and CSP (including bottom fillers for reinforcement).

[0136] [Example]

[0137] Next, the present invention will be described in more detail by way of examples. However, in the following, parts are parts by weight unless otherwise specified. In addition, the present invention is not limited to these examples. In addition, in the examples, the epoxy equivalent is measured in accordance with JIS K-7236, and the softening point is measured in accordance with the method of JIS K-7234. The softening point is measured using a softening point measuring instrument FP90 manufactured by METLER TOLEDO. The hydroxyl equivalent is determined by acetylation of the sample using acetic anhydride in a pyridine solution, decomposing the remaining anhydride with water after the acetylation, and then titrating with a 0.5N KOH ethanol solution using a potentiometric titrator to measure the amount of free acetic acid, and the hydroxyl equivalent is determined from the result.

[0138] ·GPC (Gel Permeation Chromatography) Analysis

[0139] Column: SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603 Flow rate: 1.5ml / min.

[0140] Column temperature: 40℃

[0141] Solvent used: THF (tetrahydrofuran)

[0142] Detector: RI (differential refractometer)

[0143] GC-MS (gas chromatography-mass spectrometry) analysis

[0144] Device: JMS-Q1500GC manufactured by JEOL

[0145] Column: Agilent HP-5ms 30m×0.25mm id (film thickness 0.25μm)

[0146] Carrier: He 1.5mL / min Split 1 / 30

[0147] Injection temperature: 300℃

[0148] Oven temperature: 100℃(2min)-310℃(37min) 10℃ / min heating

[0149] Ionization current: 70eV

[0150] Ionization: EI

[0151] Sample injection: 1μL

[0152] [Example 1]

[0153] In a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 100 parts of toluene, 39.1 parts of styrene, 26.5 parts of benzaldehyde, and 3.3 parts of p-toluenesulfonic acid were added while nitrogen was applied for degassing, and the temperature was raised to 120°C and reacted for 6 hours. After cooling to room temperature, 94.1 parts of phenol were added, and the reaction was carried out at 125°C for 4 hours. 100 parts of toluene were added, the organic layer was washed with water, and then concentrated until the waste liquid became neutral, and 98.2 parts of phenol resin (P1) were obtained as a brown solid component resin. The number average molecular weight Mn: 446, the weight average molecular weight Mw: 547, the hydroxyl equivalent is 212.0 g / eq, the ICI viscosity (150°C) is 0.03 Pa·s, and the softening point is 76.6°C. The GPC spectrum is shown at Figure 1 The GC-MS spectrum is shown in Figure 2 From the GC-MS analysis, it was confirmed that the phenol resin represented by the above formula (1) was produced.

[0154] [Example 2]

[0155] In a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 100 parts of toluene, 26.0 parts of styrene, 26.5 parts of benzaldehyde, and 3.3 parts of p-toluenesulfonic acid were added while nitrogen was applied for degassing, and the temperature was raised to 120°C and reacted for 4 hours. After cooling to room temperature, 94.1 parts of phenol were added and reacted at 120°C for 4 hours. The organic layer was washed with water and concentrated until the waste liquid became neutral to obtain 75.6 parts of phenol resin (P2) as a brown solid component resin. The number average molecular weight Mn: 443, the weight average molecular weight Mw: 517, the hydroxyl equivalent is 209.5 g / eq, the ICI viscosity (150°C) is 0.03 Pa·s, and the softening point is 73.2°C. The GPC spectrum is shown at Figure 3 middle.

[0156] [Example 3]

[0157] 77 parts of the phenol resin (P1) obtained in Example 1 were mixed with 100 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin and 1.8 parts of triphenylphosphine (TPP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.

[0158] [Comparative Example 1]

[0159] 100 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin and 1.4 parts of triphenylphosphine (TPP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator were prepared with respect to 39 parts of phenol novolac PN (H-1 manufactured by Meiwa Chemicals Co., Ltd.) as a phenol resin, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.

[0160] The curable resin compositions of Example 3 and Comparative Example 1 were crushed and tableted with a tableting machine. The tableted curable resin compositions were transfer molded (175° C. for 60 to 15 minutes), and after further demolding, they were cured under the conditions of 160° C. for 2 hours + 180° C. for 6 hours to obtain test pieces for evaluation.

[0161] The evaluation test pieces were measured under the following conditions. The results are shown in Table 1.

[0162] <Water absorption>

[0163] After measuring the initial mass of a disk-shaped test piece of 5 cm in diameter and 4 mm in thickness, the test piece was immersed in water at 100° C. and the mass after keeping for 24 hours was measured. The water absorption was calculated from the following formula.

[0164] Water absorption (%) = (mass after 24 hours - initial mass) / mass after 24 hours < flexural elastic coefficient >

[0165] The value was measured and calculated in accordance with JIS K-6911.

[0166] Universal tensile machine: RTG-1310 (manufactured by A&D Company, Limited)

[0167] ·Measurement temperature: 30℃

[0168] A test piece of length L = 100 mm, width W = 9 mm, and height h = 4 mm was prepared and placed across support points of distance Lv = 64 mm. The load and bending deformation when the center of the test piece was pressed by a presser were measured in an environment of 30°C.

[0169] The bending elastic coefficient E is calculated according to the following formula.

[0170] E=(L v 3 / 4Wh 3 )·(F / Y)

[0171] Here, F / Y is the slope of the straight line portion of the load / bending deformation curve (N / mm).

[0172] <Dielectric constant test and dielectric tangent test>

[0173] The dielectric constant and dielectric tangent were measured by a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by ATE Co., Ltd. The sample size was set to 1.7 mm in width×100 mm in length×1.7 mm in thickness, and the measurement temperature was set to 30°C.

[0174] [Table 1]

[0175]

[0176] From the results in Table 1, it was confirmed that Example 3 had low water absorption, high elastic modulus, low dielectric constant, and low dielectric tangent.

[0177] [Example 4]

[0178] In a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 100 parts of toluene, 26.0 parts of styrene, 26.5 parts of benzaldehyde, and 3.3 parts of p-toluenesulfonic acid were added while nitrogen was applied for degassing, and the temperature was raised to 120°C and reacted for 4 hours. After cooling to room temperature, 94.1 parts of phenol were added and reacted at 120°C for 4 hours. After washing the organic layer with water, it was concentrated until the waste liquid became neutral, and 75.6 parts of phenol resin (P3) were obtained as a brown solid component resin. The number average molecular weight Mn: 443, the weight average molecular weight Mw: 517, the hydroxyl equivalent is 209.5 g / eq, the ICI viscosity (150°C) is 0.03 Pa·s, and the softening point is 73.2°C.

[0179] [Example 5]

[0180] In a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 70 parts of the phenol resin (P3) obtained in Example 4, 123.6 parts of epichlorohydrin, 61.8 parts of dimethyl sulfoxide, and 1.3 parts of water were added while nitrogen was applied for degassing, and the internal temperature was raised to 50°C. After adding 14.3 parts of sodium hydroxide in portions over 1.5 hours, the reaction was carried out at 55°C for 2 hours and at 70°C for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under heating and reduced pressure. 150 parts of methyl isobutyl ketone (MIBK) were added, and the organic layer was washed once with 100 parts of water. The organic layer was returned to the reaction container, 4.5 parts of a 30wt% sodium hydroxide aqueous solution were added, and the reaction was carried out at 75°C for 1 hour. After cooling, the organic layer was washed 5 times with 100 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 74 parts of the target compound epoxy resin (E1) as a light yellow solid resin. The number average molecular weight Mn: 473, the weight average molecular weight Mw: 621, the epoxy equivalent is 274.3 g / eq., the ICI viscosity (150°C) is 0.02 Pa·s, and the softening point is 49.9°C. The GPC spectrum at the time of reaction termination is shown in Figure 4 The GC-MS spectrum of the target compound is shown in Figure 5From the GC-MS analysis, it was confirmed that the epoxy resin represented by the above formula (1) was produced.

[0181] [Example 6]

[0182] To 100 parts of the epoxy resin (E1) obtained in Example 5, 39 parts of a phenol resin PN (phenol novolac (H-1 manufactured by Meiwa Chemicals Co., Ltd.)) as a curing agent and 1.4 parts of triphenylphosphine (TPP manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator were mixed and kneaded uniformly using a mixing roll to obtain a curable resin composition.

[0183] [Comparative Example 2]

[0184] 42 parts of a phenol resin (phenol novolac PN (H-1 manufactured by Meiwa Chemicals Co., Ltd.)) as a curing agent and 1.4 parts of triphenylphosphine (TPP manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator were mixed and kneaded uniformly using a mixing roll to obtain a curable resin composition.

[0185] The curable resin compositions of Example 6 and Comparative Example 2 were crushed and then tableted with a tableting machine. The tableted curable resin compositions were transfer molded (175° C. for 60 to 15 minutes), and then demolded and cured under the conditions of 160° C. for 2 hours + 180° C. for 6 hours to obtain test pieces for evaluation.

[0186] The evaluation test pieces were measured under the following conditions, and the results are shown in Table 2.

[0187] <Heat resistance test (Tg)>

[0188] The glass transition temperature (temperature at which tan δ reaches a maximum value) was measured using a dynamic viscoelasticity tester.

[0189] Dynamic viscoelasticity tester: DMA-2980 manufactured by TA-instruments

[0190] Heating rate: 2℃ / min

[0191] Frequency: 10Hz

[0192] <Flexural elastic coefficient>

[0193] Measured in accordance with JIS K-6911.

[0194] Universal tensile machine: RTG-1310 (manufactured by A&D Company, Limited)

[0195] ·Measurement temperature: 30℃

[0196] Prepare a test piece with a length of L = 100mm, a width of W = 9mm, and a height of h = 4mm. Place the test piece across the support points with a distance of Lv = 64mm, and measure the load and bending deformation when the center of the test piece is pressed by a presser in an environment of 30°C, and calculate the bending elastic coefficient. <Dielectric constant test / dielectric tangent test>

[0197] The measurement was performed by the cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by ATE Co., Ltd. The sample size was set to 1.7 mm in width×100 mm in length×1.7 mm in thickness, and the measurement temperature was set to 30°C.

[0198] [Table 2]

[0199]

[0200] From the results in Table 2, it was confirmed that Example 6 had high heat resistance, high elastic modulus, low dielectric constant, and low dielectric tangent.

[0201] This application claims priority based on Japanese Patent Application No. 2021-173427 filed on October 22, 2021 and Japanese Patent Application No. 2021-173428 filed on October 22, 2021.

[0202] [Industrial Application Possibility]

[0203] The phenolic resin and epoxy resin of the present invention can be used in various composite materials, coatings, and the like, such as insulating materials for electrical and electronic components (high-reliability semiconductor packaging materials, etc.) and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.) or CFRP. In particular, they can be used in insulating materials for electrical and electronic components (high-reliability semiconductor packaging materials, etc.) and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.) that are required to have leakage resistance.

Claims

1. An epoxy resin represented by the following formula (1), In formula (1), R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is an integer from 0 to 4, q is an integer from 0 to 3, m and n are repeating numbers, and the average value of m is ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20.

2. An epoxy resin represented by the following formula (2), In formula (2), m and n are the number of repetitions, and the average value of m is ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20.

3. The epoxy resin according to claim 1 or 2, which has a weight average molecular weight of 300 to 3000 as determined by gel permeation chromatography.

4. A curable resin composition comprising the epoxy resin according to claim 1 or 2. The curable resin composition according to claim 4 , further comprising a curing agent.

6. A phenol resin represented by the following formula (3), In formula (3), R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is an integer from 0 to 4, q is an integer from 0 to 3, m and n are repeating numbers, and the average value of m is ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20.

7. A phenol resin represented by the following formula (4), In formula (4), m and n are the number of repetitions, and the average value of m is ave Satisfy 0<m ave <20, average value of n ave Satisfy 1<n ave <20.

8. The phenol resin according to claim 6 or 7, which has a weight average molecular weight of 250 to 3000 as determined by gel permeation chromatography.

9. A curable resin composition comprising the phenol resin according to claim 6 or 7. 10 . The curable resin composition according to claim 9 , further comprising an epoxy resin. 11 . The curable resin composition according to claim 5 , further comprising a curing accelerator. 12 . The curable resin composition according to claim 10 , further comprising a curing accelerator.

13. A cured product obtained by curing the curable resin composition according to claim 4.

14. A cured product obtained by curing the curable resin composition according to claim 9.

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