Curable resin composition, cured product and article

Abstract

The invention provides a curable resin composition, a cured product of the curable resin composition, and an article. The curable resin composition has dielectric properties equivalent to those of a curable resin composition containing a curing agent of an active ester resin, and has excellent adhesion to a member used in an electronic material. A curable resin composition containing an epoxy resin, a curing agent, and a basic catalyst, the curing agent containing a phenoxytriazine resin, the phenoxytriazine resin containing an oligomer of phenoxytriazine, the curing agent not having an NCO-group.

Description

Technical Field

[0001] The present invention relates to a curable resin composition, a cured product and an article. Background Art

[0002] As the amount of information communication traffic increases, electronic devices are required to process information at higher speeds and with lower power.

[0003] For example, in semiconductor sealing materials, semiconductor sealing materials with a small dielectric loss tangent (low dielectric loss tangent) have been developed in order to be used in semiconductor packaging antennas with new functions. In addition, improvements in dielectric properties are also required in circuit boards.

[0004] In these fields, curable resin compositions containing relatively inexpensive epoxy resins with excellent properties as curable resins are widely used (for example, Patent Document 1). In addition, active ester resins with excellent dielectric properties are studied as curing agents in such curable resin compositions (for example, Patent Document 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2019 / 003822

[0008] Patent Document 2: International Publication No. 2020 / 003824 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, in comparison with curable resin compositions containing conventional phenolic resin curing agents, curable resin compositions containing active ester resin curing agents have room for improvement in the adhesion between the cured product of the curable resin composition and members used in electronic materials such as copper foil.

[0011] Therefore, an object of the present invention is to provide a curable resin composition having dielectric properties equivalent to those of a curable resin composition containing a curing agent of an active ester resin and having excellent adhesion to a member used in an electronic material.

[0012] Methods for solving problems

[0013] The curable resin composition of the present invention comprises an epoxy resin, a curing agent and a basic catalyst, wherein the curing agent comprises a phenoxy triazine resin, wherein the phenoxy triazine resin comprises an oligomer of phenoxy triazine, and the curing agent does not have an NCO -Thus, the curable resin composition has dielectric properties equivalent to those of a curable resin composition containing a curing agent of an active ester resin, and has excellent adhesion to members used in electronic materials.

[0014] In one embodiment of the curable resin composition of the present invention, the oligomer has one or more selected from the group consisting of a structure represented by Formula 1 and a structure represented by Formula 2 below.

[0015] [Chemistry 1]

[0016]

[0017] In Formula 1 and 2, Ar is independently any one of Formulas 3 to 5,

[0018] [Chemistry 2]

[0019]

[0020] L is independently any one of Formulas 6 to 8,

[0021] [Chemistry 3]

[0022]

[0023] Furthermore, in Formulae 3 to 6 and 8, R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 11 carbon atoms, or a monovalent alkoxy group or aryloxy group having 1 to 11 carbon atoms,

[0024] * is the connection point with the structure of Formula 1 or 2,

[0025] In formulae 6 and 8, Y is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms.

[0026] n is an integer from 1 to 20.

[0027] The cured product of the present invention is a cured product of the above-mentioned curable resin composition.

[0028] The article of the present invention is an article comprising the above-mentioned cured product, and is an article selected from the group consisting of a prepreg film and a semiconductor sealing material.

[0029] Effects of the Invention

[0030] According to the present invention, there can be provided a curable resin composition having dielectric properties equivalent to those of a curable resin composition containing a curing agent of an active ester resin and having excellent adhesion to a member used for an electronic material. DETAILED DESCRIPTION

[0031] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of illustrating the present invention, and do not limit the present invention in any way.

[0032] In the present invention, two or more embodiments can be arbitrarily combined.

[0033] Unless otherwise specified, the materials, components, compounds, resins, catalysts, and solvents described in the present specification may be used alone or in combination of two or more.

[0034] In the present specification, the expression "a group having a valence of X" such as a monovalent hydrocarbon group, a monovalent alkoxy group, a monovalent aryloxy group, etc. means that the number of bonds of the group with respect to other atoms, groups or structures is X. A "substituent containing a monovalent phenolic hydroxyl group" means that the number of bonds of the substituent containing a phenolic hydroxyl group itself with respect to other atoms, groups or structures is 1. A "substituent containing a divalent phenolic hydroxyl group" means that the number of bonds of the substituent containing a phenolic hydroxyl group itself with respect to other atoms, groups or structures is 2.

[0035] In this specification, when a certain group or compound has one phenolic hydroxyl group, it is referred to as having a "phenolic hydroxyl group with a monovalent hydroxyl group". When a certain group or compound has two phenolic hydroxyl groups, it is referred to as having a "phenolic hydroxyl group with a divalent hydroxyl group". When a certain group or compound has three or more phenolic hydroxyl groups, it is referred to as having a "phenolic hydroxyl group with a polyvalent hydroxyl group".

[0036] (Curable resin composition)

[0037] The curable resin composition of the present invention comprises an epoxy resin, a curing agent and a basic catalyst, wherein the curing agent comprises a phenoxy triazine resin, wherein the phenoxy triazine resin comprises an oligomer of phenoxy triazine, and the curing agent does not have an NCO - base.

[0038] Epoxy resin

[0039] As epoxy resin, there is no particular limitation, and known epoxy resins can be used. As epoxy resin, for example, bisphenol epoxy resin, biphenyl epoxy resin, novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, etc. can be cited. In addition, epoxy resins described in Japanese Patent Publication No. 2021-102702 can also be used.

[0040] Examples of the novolac epoxy resin include phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxides of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, and biphenyl novolac epoxy resins.

[0041] From the viewpoint of increasing the glass transition temperature of the cured product of the curable resin composition and improving heat resistance, the epoxy equivalent of the epoxy resin is preferably 1,000 g / equivalent or less, particularly preferably 700 g / equivalent or less, and particularly preferably 500 g / equivalent or less.

[0042] Curing agent

[0043] The curing agent of the curable resin composition of the present invention comprises a phenoxy triazine resin, the phenoxy triazine resin comprises an oligomer of phenoxy triazine, and the curing agent does not have an NCO - Group (cyanate group).

[0044] The phenoxytriazine resin includes a phenoxytriazine oligomer. Examples of the triazine forming the phenoxytriazine include 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine. In a preferred embodiment, the triazine forming the phenoxytriazine is 1,3,5-triazine.

[0045] In one embodiment of the curable resin composition of the present invention, the oligomer has a structure represented by the following General Formula 1.

[0046] [Chemistry 4]

[0047]

[0048] In Formula 1 and 2, Ar is independently any one of Formulas 3 to 5,

[0049] [Chemistry 5]

[0050]

[0051] L is independently any one of Formulas 6 to 8,

[0052] [Chemistry 6]

[0053]

[0054] In Formulae 3 to 6 and 8, R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 11 carbon atoms, or a monovalent alkoxy or aryloxy group having 1 to 11 carbon atoms.

[0055] In Formulae 3 to 8, * is the connection point with the structure of Formulae 1 or 2,

[0056] In formulae 6 and 8, Y is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms.

[0057] n is an integer from 1 to 20.

[0058] Examples of the compound that forms Ar include compounds of the following formulae 9 to 11.

[0059] [Chemistry 7]

[0060]

[0061] In the formula, R has the same meaning as R in formulas 3 to 5.

[0062] From the viewpoint of solubility of the oligomers of Formulae 1 and 2 in solvents, R is preferably a monovalent hydrocarbon group having 1 to 11 carbon atoms or a monovalent alkoxy or aryloxy group having 1 to 11 carbon atoms. More preferably, R is methyl, ethyl, propyl, tert-butyl, phenyl, benzyl, methoxymethyl, or allyl.

[0063] In a preferred embodiment, the compound forming Ar is at least one selected from the group consisting of 2-allylphenol, cresol, o-phenylphenol and 2-allyl-1-naphthol.

[0064] In a preferred embodiment, Ar is represented by the following formula 12.

[0065] [Chemistry 8]

[0066]

[0067] In a preferred embodiment, the compound forming L is the following compound 1.

[0068] [Chemistry 9]

[0069]

[0070] In another preferred embodiment, the compound forming L is the following compound 2.

[0071] [Chemistry 10]

[0072]

[0073] In a preferred embodiment, L is the following formula 13.

[0074] [Chemistry 11]

[0075]

[0076] In another embodiment, the compound forming Ar may have two or more phenolic hydroxyl groups, for example, 2, 3 or 4. Examples of the compound having two or more phenolic hydroxyl groups include compounds represented by the following formulae 14 to 21.

[0077] [Chemistry 12]

[0078]

[0079] In formulas 14 to 21, R 2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, n represents 1, 2 or 3, and p represents an integer of 1 or greater.

[0080] As R 2 The alkyl group of R includes, for example, an alkyl group having 1 to 20 carbon atoms. 2 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl.

[0081] As R 2 Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

[0082] p in Formula 17 is an integer greater than or equal to 1, preferably an integer of 1-20, more preferably an integer of 1-15, and even more preferably an integer of 1-12.

[0083] In another embodiment, the compound forming Ar may be a multifunctional phenol compound. The multifunctional phenol compound may be a compound represented by the following Formula 22.

[0084] [Chemistry 13]

[0085]

[0086] In formula 22, Ar 1 Each independently represents a substituent containing a monovalent phenolic hydroxyl group, Ar 2 Each independently represents a substituent containing a divalent phenolic hydroxyl group, Z each independently represents an oxygen atom, a sulfur atom, a keto group, a sulfonyl group, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms, and m is an integer of 0 to 20.

[0087] As the formation of Ar 1 The compounds include, for example, the compounds represented by the following formulas 23 and 24.

[0088] [Chemistry 14]

[0089]

[0090] In formula 23 and 24, R 3 Each of them is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; and n is 0, 1, 2, 3 or 4.

[0091] R 3 The alkyl and aryl groups with R 2 same.

[0092] Examples of the alkylene group having 1 to 20 carbon atoms in Z of Formula 22 include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, and hexylene.

[0093] Examples of the cycloalkylene group having 3 to 20 carbon atoms in Z of Formula 22 include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cycloalkylene groups represented by the following Formulas 25 to 28.

[0094] [Chemistry 15]

[0095]

[0096] In formula 25~28, * represents the 1 or Ar 2 connection point.

[0097] Examples of the arylene group having 6 to 20 carbon atoms in Z of Formula 22 include the arylene group represented by Formula 29.

[0098] [Chemistry 16]

[0099]

[0100] In formula 29, * represents the 1 or Ar 2 connection point.

[0101] Examples of the aralkylene group having 8 to 20 carbon atoms in Z of Formula 22 include the aralkylene groups represented by the following Formulas 30 to 34.

[0102] [Chemistry 17]

[0103]

[0104] In formulas 30 to 34, * represents the 1 or Ar 2 connection point.

[0105] Z in Formula 22 is preferably a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms, and is more preferably a group represented by Formula 27, 28, 29, 30, 31, 32, 33 or 34 from the viewpoint of adhesion and dielectric properties.

[0106] In Formula 22, m is 0 or an integer of 1 to 20, preferably 0, 1, 2, 3, 4, 5, 6, 7 or 8, and is preferably 0, 1, 2, 3, 4 or 5 from the viewpoint of solubility of the oligomers of Formulas 1 and 2 in solvents.

[0107] From the viewpoint of solvent solubility and dielectric properties of the reaction product, the compounds represented by Formula 21, 22, and 17 are preferred. Furthermore, in Formula 22, Ar 1 It is a residue of phenol, o-cresol, xylenol, phenylphenol, or α-naphthol, β-naphthol, and Z is a compound represented by Formula 27, 29, 30, 31, 32, 33 or 34, and more preferably a compound represented by Formula 17.

[0108] In Formulae 1 and 2, n is an integer of 1 to 20. Preferably, n is an integer of 1 to 10.

[0109] In one embodiment, the oligomer of phenoxytriazine has structure 3 below.

[0110] [Chemistry 18]

[0111]

[0112] The curing agent of the curable resin composition of the present invention may contain oligomers of phenoxy triazine, may contain monomers of phenoxy triazine, or may not contain monomers of phenoxy triazine. The ratio of the monomers of phenoxy triazine is, for example, 1 to 90% by mass relative to the total mass of the monomers and oligomers of phenoxy triazine. When the ratio of the monomers of phenoxy triazine is 1% by mass or more relative to the total mass of the monomers and oligomers, the fluidity is improved, and when it is 90% by mass or less, the heat resistance is improved.

[0113] The amount of the curing agent is preferably in the range of 0.1 to 5.0 phenoxy groups in the phenoxy triazine group of the curing agent relative to 1 equivalent of the epoxy group in the epoxy resin. Within this range, curability, heat resistance, and dielectric properties are good.

[0114] Basic catalyst

[0115] The alkaline catalyst is not particularly limited, and a known alkaline catalyst can be used. Examples of the alkaline catalyst include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), imidazole, 1-methylimidazole, 2,4-dimethylimidazole, and 1,4-diethylimidazole. In addition, examples thereof include alkaline catalysts and amine curing accelerators described in Japanese Patent Application Publication No. 2023-037521 and alkaline catalysts and amine curing accelerators described in Japanese Patent Application Publication No. 2023-090562.

[0116] In a preferred embodiment, the basic catalyst is one or more selected from the group consisting of imidazoles and DMAP. In another preferred embodiment, the basic catalyst is one or more selected from the group consisting of imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole and DMAP.

[0117] The amount of the alkaline catalyst can be appropriately adjusted, for example, 0.01 to 5.0 parts by mass relative to 100 parts by mass of the total of the curing agent and the epoxy resin. When the amount of the alkaline catalyst is 0.01 parts by mass or more, the curability is excellent. On the other hand, when the amount of the alkaline catalyst is 5.0 parts by mass or less, the insulation reliability is excellent.

[0118] Other ingredients

[0119] The curable resin composition may further contain a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, an emulsifier, a solvent, other resins (ie, resins other than the epoxy resin), and the like.

[0120] As other resins, for example, maleimide resins etc. can be mentioned. In addition, for example, other resins described in Japanese Patent Application Laid-Open No. 2023-090562 can also be used. The content of other resins in the curable resin composition of the present embodiment is preferably 50% by mass or less of the entire resin.

[0121] ·Method for preparing curable resin composition

[0122] The method for preparing the curable resin composition is not particularly limited, and the curable resin composition can be obtained by mixing an epoxy resin, a curing agent, and a basic catalyst.

[0123] ·Application of curable resin composition

[0124] Examples of uses of the curable resin composition include printed wiring board materials, resin compositions for flexible wiring substrates, interlayer insulating materials for build-up substrates, insulating materials for circuit substrates such as adhesive films for build-up, resin casting materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. In addition, examples include uses described in Japanese Patent Gazette No. 7188657.

[0125] ·Cured product

[0126] The cured product of the present invention is a cured product of the curable resin composition described above. The cured product of the present invention has dielectric properties equivalent to those of a cured product of a curable resin composition containing an active ester resin as a curing agent, and has excellent adhesion to members used in electronic materials.

[0127] As a method for obtaining a cured product, for example, the curable resin composition may be cured by heating. The temperature during the heat curing is, for example, 100 to 300° C. The heating time is, for example, 1 to 24 hours.

[0128] ·thing

[0129] In one embodiment, the article of the present invention is an article comprising the above-mentioned cured product, and the article is an article selected from the group consisting of a varnish, a prepreg, a film, and a semiconductor sealing material.

[0130] Example

[0131] Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are for the purpose of illustrating the present invention and do not limit the present invention in any way.

[0132] The materials used in the examples are as follows.

[0133] Epoxy resin: cresol novolac type epoxy resin, product name "EPICLON (registered trademark) N-655-EXP-S" manufactured by DIC Corporation, softening point 58°C, epoxy equivalent 202 g / equivalent.

[0134] Curing agent: synthesized by the method described below.

[0135] Basic catalyst: 4-dimethylaminopyridine (DMAP).

[0136] Addition polymerization resin of dicyclopentadiene and phenol based on Friedel-Crafts reaction, containing about 80% by mass of Compound 1: hydroxyl equivalent: 165 g / equivalent, softening point 85°C.

[0137] [Chemistry 19]

[0138]

[0139] Fused silica: manufactured by Denka Corporation, product name “FB-560”.

[0140] Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-403”.

[0141] Release agent: manufactured by Dainichi Chemical Co., Ltd. Product name: "F1-100".

[0142] Synthesis of curing agent

[0143] Add 111.5 g of cyanuric chloride and 923 g of toluene to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer. The system is replaced with nitrogen under reduced pressure to dissolve cyanuric chloride in toluene. Next, 162.4 g of allyl phenol and 100 g of a polyaddition reaction resin of dicyclopentadiene and phenol are added to the solution, and the system is replaced with nitrogen under reduced pressure to dissolve it. Then, 0.5 g of tetrabutylammonium bromide is dissolved in the solution. While nitrogen is purged in the system, the system is controlled at below 60°C. Next, 363.6 g of a 20% aqueous sodium hydroxide solution is added dropwise to the solution over 3 hours. Then, stirring is continued for 1.0 hour while maintaining the conditions. After the reaction is completed, the flask is allowed to stand, the liquid is separated, and the water layer is removed. Then, water is added to the toluene layer, mixed for about 15 minutes, allowed to stand, the liquid is separated, and the water layer is removed. Repeat this operation until the pH of the water layer reaches 7. Then, the toluene layer in the flask was dried under reduced pressure with heat to obtain a phenoxy triazine resin as a curing agent and having structure 3. The softening point of the phenoxy triazine resin was 68° C. The phenoxy triazine resin had no NCO - base.

[0144] Synthesis of Comparative Curing Agent 1

[0145] Add 165.0 g of the addition polymerization resin of dicyclopentadiene and phenol, 134.0 g (1.0 mole) of allylphenol and 1048 g of toluene to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer. The system is replaced with nitrogen under reduced pressure, and the addition polymerization resin and allylphenol are dissolved in toluene. Next, 203 g (1.0 mole) of isophthaloyl chloride is added to the solution, and the system is replaced with nitrogen under reduced pressure to dissolve the isophthaloyl chloride. Then, while nitrogen is purged in the system, the system is controlled at below 60°C. Next, 373 g of a 20% aqueous sodium hydroxide solution is added dropwise to the solution over 3 hours. Then, stirring is continued for 1.0 hour while maintaining the conditions. After the reaction is completed, the flask is allowed to stand for separation and the water layer is removed. Then, water is added to the toluene layer, mixed for about 15 minutes, allowed to stand, separated, and the water layer is removed. This operation was repeated until the pH of the water layer reached 7. Then, the toluene layer in the flask was dried under reduced pressure with heat to synthesize an active ester resin as a comparative curing agent. The active ester resin had an esterification equivalent of 215 g / equivalent and a softening point of 80°C.

[0146] Synthesis of Comparative Curing Agent 3

[0147] Synthesis was performed in the manner described in Example 1 of International Publication No. 2019 / 198606 to obtain 2,4,6-tri(allylphenoxy)-s-triazine (molecular weight 478) as the comparative curing agent 3, i.e., the phenoxytriazine monomer 2.

[0148] Preparation of curable resin composition (Example 1 and Comparative Example 1)

[0149] The cresol novolac epoxy resin and the obtained curing agent resin were weighed at the mass ratio shown in Table 1 so that each functional group was equal. Then, the cresol novolac epoxy resin and the curing agent resin were heated and melted at 150° C., and then mixed and homogenized. DMAP in the amount shown in Table 1 was added to the mixture, and further stirred and homogenized. Then, the mixture was cooled to obtain a curable resin composition.

[0150] Comparative Example 2

[0151] As phenoxy triazine monomer 1, 37.1 parts by mass of 2,4,6-triphenoxy-1,3,5-triazine (molecular weight 357) and 62.9 parts by mass of cresol novolac epoxy resin were mixed while heating at 150°C, but the mixture was cloudy and could not be uniformly dissolved. In addition, homogenization was attempted using methyl ethyl ketone and toluene, using 62.9 parts by mass of the same amount as the epoxy resin, but phenoxy triazine monomer 1 did not dissolve. Therefore, it was not possible to prepare a curable resin composition suitable for measuring physical properties, and thus physical properties were not measured.

[0152] Comparative Example 3

[0153] 44.1 parts by mass of comparative curing agent 3 and 55.9 parts by mass of cresol novolac epoxy resin were mixed while heating at 150° C. A predetermined amount of DMAP was added as a catalyst, and the mixture was further stirred to be homogenized. Then, the mixture was cooled to obtain a curable resin composition.

[0154] ·Test pieces for measuring Tg and dielectric properties

[0155] The obtained curable resin composition was placed in a mold, heated at 180°C for 30 minutes using a hot press, and then temporarily removed. Next, the curable resin composition was further heated at 200°C for 2 hours to obtain a cured product. The cured product was cut into a predetermined size and used as a test piece 1.

[0156] ·Tg determination

[0157] Using a viscoelasticity measuring device (DMA: RSA II solid viscoelasticity measuring device manufactured by Rheometrics), under the conditions of the rectangular tension method, a frequency of 1 Hz, and a heating rate of 3°C / min, the temperature at which the ratio of the change in elastic modulus to the change in viscoelastic modulus was maximized (tan δ was the maximum) was evaluated as the glass transition temperature.

[0158] The curable resin composition of Comparative Example 3 was placed in a mold, heated at 180°C for 30 minutes using a hot press, and then the temporarily removed product was further heated at 200°C for 2 hours to obtain a cured product. The glass transition temperature was measured by DMA to be 108°C, which was significantly worse than that of the examples.

[0159] ·Determination of dielectric properties

[0160] In accordance with JIS C 6481, the dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz were measured using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc., after the test piece was dried by placing it in a hot air dryer at 105°C for 2 hours and then stored in a room at 23°C and 50% humidity for 24 hours.

[0161] Chip shear test

[0162] 30 parts by mass of curable resin composition, 30 parts by mass of fused silica, 0.3 parts by mass of silane coupling agent, and 0.45 parts by mass of release agent were mixed. The mixture was transfer molded into a specified size on a copper substrate at 175°C, 120 seconds, and a molding pressure of 6.9 MPa, and further heated at 200°C for 2 hours to complete the curing reaction and obtain a test piece 2. The test piece 2 was used to perform a chip shear test. The details of the chip shear test are as follows.

[0163] The test piece 2 was crushed and pulverized using a transfer molding machine at a pressure of 70 kg / cm 2 , punching speed 5cm / sec, temperature 175℃, time 600 seconds, the molded product size is 2mm thick and 4mm×4mm, 6mm×6mm, 8mm×8mm, 10mm×10mm, and 4 test pieces are formed on copper foil to obtain 4 test pieces. The test was carried out using an adhesion tester ("PTR-1102" manufactured by RHESCA). The shear rate was 0.1mm / sec, and the test was carried out 5 times for each test piece, and the average value (kgf) of the peel strength from the copper foil was calculated. The copper foil used was "EFTEC-64T" (thickness 0.15mm) manufactured by Furukawa Electric Industries.

[0164] The curable resin composition of Comparative Example 3 had strong tackiness and was in a semisolid to viscous liquid state. Since it was difficult to handle as a solid, transfer molding could not be performed.

[0165] [Table 1]

[0166]

[0167] Industrial Applicability

[0168] According to the present invention, it is possible to provide a curable resin composition having dielectric properties equivalent to those of a curable resin composition containing a curing agent of an active ester resin and having excellent adhesion to a member used in an electronic material.

Claims

1. A curable resin composition comprising an epoxy resin, a curing agent and a basic catalyst, The curing agent comprises a phenoxy triazine resin, The phenoxy triazine resin comprises an oligomer of phenoxy triazine, The curing agent does not have NCO - base.

2. The curable resin composition according to claim 1, wherein The oligomer has one or more selected from the group consisting of the structure represented by the following formula 1 and the structure represented by the following formula 2, [Chemistry 1] In the formula, Ar each independently represents any one of Formulas 3 to 5, [Chemistry 2] L is independently any one of Formulas 6 to 8, [Chemistry 3] In Formulae 3 to 6 and 8, R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 11 carbon atoms, or a monovalent alkoxy or aryloxy group having 1 to 11 carbon atoms. In Formulae 3 to 8, * is the connection point with the structure of Formulae 1 or 2, In formulae 6 and 8, Y is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms. n is an integer from 1 to 20.

3. The curable resin composition according to claim 2, wherein Ar is Formula 3.

4. The curable resin composition according to claim 2, wherein L is formula 13, [Chemistry 4] 。 5 . A cured product, which is a cured product of the curable resin composition according to claim 1 . 6 . An article comprising the cured product according to claim 5 , wherein the article is selected from the group consisting of a prepreg film and a semiconductor sealing material.

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