JP2023138435A - Epoxy resin, curable resin composition and cured product thereof, and polyhydric hydroxy resin - Google Patents

Abstract

To provide an epoxy resin that excels in low water absorbency and flame retardancy, a curable resin composition and a cured product thereof, and a polyhydric hydroxy resin that serves as the raw material for the epoxy resin.SOLUTION: The present invention provides an epoxy resin represented by formula (1). (In formula (1), G represents a glycidyl group. R1's independently represent a hydrogen atom or a C1-6 hydrocarbon group. A plurality of R2's each represent a substituent derived from a substitution reaction with an α-methyl styrene. Each p represents a real number of 0-3. n represents the number of repetitions. The average value of n, nave, is expressed as 1≤nave≤20.)SELECTED DRAWING: Figure 9

Description

The present invention relates to an epoxy resin, a curable resin composition, a cured product thereof, and a polyhydric hydroxy resin.

In recent years, with advances in the electrical and electronic fields, there has been a demand for the development of higher performance resin compositions. In particular, semiconductor encapsulation and substrates (the substrate itself or its surrounding materials) such as CPUs are becoming thinner in accordance with the evolution of semiconductors, and the actual operating temperature range (room temperature to 100°C, non-patent document 1) There is a need for a material that can suppress warping on both sides at high temperatures (260°C) during free solder reflow. Specifically, there is a need for a material that has a high elastic modulus that can withstand the heat generated during driving at the actual operating temperature, and a low elastic modulus that can offset stress due to expansion at high temperatures (Non-Patent Document 2). In addition, in recent years, as in-vehicle materials have become more electrically equipped, environmental resistance in terms of electrical reliability has also been required, and moisture absorption resistance such as MSL (Moisture Sensitivity Level) has become important. MSL is a standard established by the JEDEC (Joint Electron Device Engineering Council), which was established with the aim of preventing the phenomenon of damage caused by volumetric expansion due to moisture evaporation during reflow, etc., due to the absorption of moisture in the air by the sealing resin for semiconductor packages. ) standard.

Furthermore, from the perspective of reducing environmental impact, there is a movement to eliminate halogen-based flame retardants, and base resins with even better flame retardancy are being sought.

Special Publication No. 55-010612

Takeshi Nishi, Thermal design, thermal control, and heat transfer of microprocessors for notebook personal computers, October 2020, pp. 3-8 Nozomi Takano et al., Low thermal expansion/high elastic modulus substrate material for semiconductor packaging, Journal of Electronics Packaging Society, Vol. 3 NO. 3, 2000, pp. 210-214.

Aromatic substituents are assumed to be effective as a measure to achieve the above characteristics. Patent Document 1 discloses an epoxy resin of p-cumylphenol-formaldehyde. However, when formaldehyde is used in excess, alcoholic hydroxyl groups remain at the ends, making it difficult to completely epoxidize. On the other hand, if p-cumylphenol is used in excess, p-cumylphenol monomer remains, making it impossible to achieve sufficient properties.

The present invention was made in view of the above circumstances, and provides an epoxy resin with low water absorption and excellent flame retardancy, a curable resin composition, a cured product thereof, and a polyvalent hydroxy resin that is a raw material for the epoxy resin. The purpose is to

That is, the present invention relates to the following [1] to [8]. In the present invention, "(numerical value 1) to (numerical value 2)" indicates that the upper and lower limits are included.
[1]
An epoxy resin represented by the following formula (1).

(In formula (1), G represents a glycidyl group. Plural R ₁ 's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Plural R ₂ 's are represented by the following formula (1 Indicates a substituent represented by -a).The plural ps are each a real number from 0 to 3, and the average p _ave is 0.1≦p _ave ≦3.0.n is the number of repetitions. and the average value n _ave of n is 1≦n _ave ≦20.)

(In formula (1-a), a plurality of R _3s exist independently and represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0.01≦q _ave ≦3.0. The wavy line indicates the binding site.)
[2]
Epoxy equivalent is 265g/eq. More than 320g/eq. The epoxy resin described in the following item [1].
[3]
The epoxy resin according to item [1] or [2] above, which has a softening point of 50°C or more and 90°C or less.
[4]
A curable resin composition comprising the epoxy resin according to any one of [1] to [3] above and a curing agent.
[5]
The curable resin composition according to item [4], further containing a curing accelerator.
[6]
A cured product obtained by curing the curable resin composition according to item [4] or [5].
[7]
A semiconductor encapsulating material obtained by curing the curable resin composition according to item [4] or [5].
[8]
A polyhydric hydroxy resin represented by the following formula (2).

(In formula (2), multiple R ₁ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and multiple R ₂ 's are substituted by the following formula (2-a). The plurality of ps are each a real number from 0 to 3, and the average value p _ave of p is 0.1≦p _ave ≦3.0. n is the number of repetitions, and the average value n of n _ave is 1≦n _ave ≦20.)

(In formula (2-a), a plurality of R ₃ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0. 01≦q _ave ≦3.0. The wavy line indicates the binding site.)

The epoxy resin and curable resin composition of the present invention have excellent low water absorption and flame retardancy, and can be suitably used as sealing materials for electrical and electronic components and CFRP. be.

2 is a GPC chart of Example 1. 1 is an LC-MS chart of Example 1. 1 is a ^1H -NMR chart of Example 1. 3 is a GPC chart of Example 2. 3 is an LC-MS chart of Example 2. 3 is a GPC chart of Example 3. 12 is a ^1H -NMR chart of Example 3. It is a GPC chart of Example 4. 3 is a DMA chart of Example 5 and Comparative Examples 1 to 3.

The epoxy resin of this embodiment is represented by the following formula (1), and the curable resin composition containing the epoxy resin of this embodiment has high elasticity in the practical use temperature range (room temperature to 100°C). It has low elasticity at high temperatures (near 260°C), low water absorption, and excellent flame retardancy.

(In formula (1), G represents a glycidyl group. Plural R ₁ 's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Plural R ₂ 's are represented by the following formula (1 Indicates a substituent represented by -a).The plural ps are each a real number from 0 to 3, and the average p _ave is 0.1≦p _ave ≦3.0.n is the number of repetitions. and the average value n _ave of n is 1≦n _ave ≦20.)

(In formula (1-a), a plurality of R _3s exist independently and represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0.01≦q _ave ≦3. The wavy line indicates the binding site.)

In the formula (1), R ₁ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or a methyl group. is more preferable, and a hydrogen atom is particularly preferable.

In the formula (1-a), R ₃ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group. It is more preferable that it is, and it is especially preferable that it is a hydrogen atom.

In the above formula (1), p is a real number from 0 to 3, and the average value p _ave of p is 0.1≦p _ave ≦3.0, but 0.1≦p _ave ≦2.0. It is preferable that p ave be 0.1≦p _ave ≦1.5. If p _ave is 0.1 or more, the elastic modulus, low water absorption, and flame retardance will be good, and if p _ave is 3 or less, the functional group density will be high and the curability will be good. When 0.1≦p _ave ≦0.9, it is particularly preferable because it is possible to obtain a low-viscosity epoxy resin with high elastic modulus and low water absorption without impairing heat resistance.

In the formula (1-a), q is the number of repetitions, and the average value q _ave of q is 0.01≦q _ave ≦3.0, but 0.01≦q _ave ≦2.0. It is preferable that q ave be 0.01≦q _ave ≦1.0. If q _ave is 0.01 or more, the elastic modulus, low water absorption, and flame retardance will be good, and if q _ave is 3 or less, the functional group density will increase and the curability will be good.

The values of p _ave and q _ave are the peak of 3.5 to 3.9 ppm in the ¹ H-NMR chart of the epoxy resin, the peak of methylene group hydrogen derived from the polyhydric hydroxy resin as the raw material, and the peak of 2.1 to 2.4 ppm of hydrogen. It can be calculated from the respective peak areas when the peak is assigned to the methylene group hydrogen in (1-a) and the peak at 1.3 to 1.7 ppm is assigned to the methyl group hydrogen in (1-a). Since the values of p _ave and q _ave are almost the same as the values of p _ave and q _ave of the polyvalent hydroxy resin represented by the above formula (2), ^{the 1} H-NMR chart of the polyvalent hydroxy resin A value calculated from the measurement results may be used.

In the above formula (1), the average value n _ave is the number average molecular weight (Mn) determined by gel permeation chromatography (GPC, detector: RI) measurement of epoxy resin, or the value of the separated peak. It can be calculated from the area ratio of each. In addition, the value of n _ave is almost the same as the value of n _ave of the polyvalent hydroxy resin represented by the above formula (2) and the polyvalent hydroxy resin represented by the following formula (3), which will be described later. , a value calculated from the measurement results of a polyvalent hydroxy resin represented by the above formula (2) or a polyvalent hydroxy resin represented by the following formula (3) may be used. n _ave is usually 1≦n _ave ≦20, preferably 1.1≦n _ave ≦10, and more preferably 5≦n _ave ≦9. The number average molecular weight is preferably 200 or more and less than 5,000, more preferably 300 or more and less than 3,000, and particularly preferably 400 or more and less than 2,000. When the weight average molecular weight is less than 5,000, purification by washing with water becomes easy, and when it is 200 or more, the target compound does not volatilize in the solvent distillation step.

In the present invention, gel permeation chromatography analysis is performed under the following conditions.

・GPC (gel permeation chromatography) analysis Manufacturer: Shimadzu Column: Guard column KF-G4A GPC KF-601 (1 piece), KF-602 KF-602.5, KF-603
Flow rate: 1.5ml/min.
Column temperature: 40℃
Solvent used: THF (tetrahydrofuran)
Detector: RID-20A (differential refraction detector)

The epoxy equivalent of the epoxy resin of this embodiment is 265 g/eq. More than 320g/eq. It is preferably less than 270g/eq. More than 310g/eq. It is more preferable that it is less than Epoxy equivalent is 265g/eq. If it is above, the water absorption will be low, 320g/eq. If it is below, the heat resistance will be good.

The epoxy resin of this embodiment preferably has a resin-like form having a softening point, and the softening point is preferably 50°C or more and 90°C or less. If the softening point is less than 50°C, handling of the product will be difficult due to blocking, and if it exceeds 90°C, it will not be possible to fill the product with a high degree of filler, and a sufficient warpage suppressing effect will not be obtained.

The epoxy resin represented by the above formula (1) (hereinafter also referred to as AMSPNE) is an α,α-dimethylbenzyl group-added polyhydric hydroxy resin (hereinafter also referred to as AMSPN) represented by the following formula (2). It can be obtained by epoxidizing it by a known method.

(In formula (2), multiple R ₁ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and multiple R ₂ 's are substituted by the following formula (2-a). The plurality of ps are each a real number from 0 to 3, and the average value p _ave of p is 0.1≦p _ave ≦3.0. n is the number of repetitions, and the average value n of n _ave is 1≦n _ave ≦20.)

(In formula (2-a), a plurality of R ₃ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0. 01≦q _ave ≦3.0. The wavy line indicates the binding site.)

R ₁ , R ₂ , R ₃ , p _ave , q _ave , n _ave and their preferred ranges in the formulas (2) and (2-a) are the same as in the formulas (1) and (1-a). .

AMSPN can be obtained by subjecting a polyhydric hydroxy resin represented by the following formula (3) to an addition reaction with α-methylstyrenes or α-cumyl alcohol represented by the following formula (4).

(In formula (3), multiple R ₁ 's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n is the repeating number, and the average value n _ave of n is 1≦n _ave ≦20.)

(In formula (4), multiple R ₃ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0.01≦ q _ave ≦3.0.)

R ₁ , R ₃ , p, q, n and their preferred ranges in formulas (3) and (4) are the same as in formulas (1) and (1-a).

AMSPN is produced by first adding α-methylstyrenes or α-cumyl alcohol represented by the above formula (4) to the phenolic aromatic ring of the polyhydric hydroxy resin represented by the above formula (3). The hydroxyl equivalent can be arbitrarily adjusted by Here, adding α-methylstyrene or α-cumyl alcohol represented by the above formula (4) means that the hydrogen of the benzene ring of the polyhydric hydroxy resin represented by the above formula (3) and the formula (2 - Refers to substituting a substituent represented by a). In other words, in cured epoxy resin products, it is said that hydroxyl groups, which are hydrophilic functional groups produced by the reaction between epoxy groups and hydroxyl groups, affect water absorption. The proportion of hydrophilic functional groups is reduced, and a high degree of moisture resistance can be achieved. In addition, by adding a highly aromatic substituent represented by formula (2-a), aromaticity is further improved, and in addition to further improving moisture resistance, flame retardancy is also improved. is also effective.

Therefore, the epoxy resin synthesized from AMSPN has high elasticity in the actual usage temperature range (room temperature to 100°C), low elasticity at high temperatures (260°C), and also has high moisture resistance and flame retardancy. Excellent in sex.

During the addition reaction between the polyhydric hydroxy resin represented by the formula (3) and the α-methylstyrenes represented by the formula (4), the ratio of the polyhydric hydroxy resin to the α-methylstyrenes is Considering the balance between flame retardancy and curability of the resulting cured product, the ratio of α-methylstyrenes to be used is 0.1 to 2.5 moles per mole of phenolic aromatic ring in the polyhydric hydroxy resin. The amount is preferably in the range of 0.1 to 1.0 mol, and even more preferably 0.3 to 0.8 mol. If it is 0.1 or more, the elastic modulus, low water absorption, and flame retardance will be good, and if it is 2.5 or less, the functional group density will increase and the curability will be good. This molar ratio is related to p in formula (2) and q in formula (2-a).

The polyhydric hydroxy resin represented by formula (3) is typically phenol novolak or cresol novolak, but phenol novolak is more preferred. When a cresol novolak is used, o-cresol, m-cresol, and p-cresol novolaks may be included.

The α-methylstyrene represented by the formula (4) is α-methylstyrene, α-methylstyrene substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a polymerized compound thereof, and preferably α-methylstyrene - It is a compound in which methylstyrene or α-methylstyrene is polymerized.

In the addition reaction between the polyhydric hydroxy resin represented by the formula (3) and the α-methylstyrene represented by the formula (4), it is preferable to use an acid catalyst, and the acid catalyst may be a well-known inorganic acid, It can be appropriately selected from organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfate, and diethyl sulfate, zinc chloride, aluminum chloride, iron chloride, trifluorocarbon Examples include Lewis acids such as boron oxide, ion exchange resins, solid acids such as activated clay, silica-alumina, and zeolite. These acid catalysts may be used alone or in combination of two or more.

The amount of these acid catalysts used can be selected in the range of 10 to 1000 ppm, preferably in the range of 100 to 500 ppm. If the amount is more than this, the crosslinks of the generated isopropylidene groups tend to be partially cleaved, and the properties of the raw material polyhydric hydroxy resin tend to remain unimproved. On the other hand, if the amount is less than this, the reactivity decreases and a large amount of unreacted α-methylstyrene monomer remains. Furthermore, when adding these acid catalysts into the reaction system, it is also possible to add them in advance to a heated melt of phenols, or to dilute them with a suitable solvent and then gradually add them.

These condensation reactions in the presence of an acid catalyst are preferably carried out at a temperature in the range of 40 to 120°C. If it is lower than this, the reactivity decreases and the reaction time becomes long. Moreover, if it is higher than this, the crosslinking bonds of the generated isopropylidene groups are likely to be partially cleaved, and the properties of the raw material polyhydric hydroxy resin tend to remain unimproved. The reaction time can usually be selected within the range of 1 to 20 hours.

AMSPN is obtained by a concerted reaction of substitution reaction of α-methylstyrenes on a phenolic aromatic ring and polymerization reaction of α-methylstyrenes, and therefore contains various components. For example, a structure in which two α-methylstyrenes are bound to a phenolic aromatic ring or a structure in which one α-methylstyrene dimer is bound can be obtained with the same molecular weight.
The specific method for carrying out this reaction is to charge all the raw materials at once and allow the reaction to proceed as is at a predetermined temperature, or to charge the polyhydric hydroxy resin and catalyst and maintain the α- A common method is to react while dropping methylstyrene. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. After the reaction, if a solvent is used, the resin used in the present invention can be obtained by distilling off the solvent after removing the catalyst component if necessary; if a solvent is not used, it can be directly discharged during heating. By doing this, the target AMSPN can be obtained.

Next, the reaction for obtaining the epoxy resin of this embodiment will be explained.
The epoxy resin of this embodiment is obtained by epoxidizing the above AMSPN using a known method. Examples include reactions with epihalohydrins and oxidation reactions of olefins.

The epihalohydrin is easily available on the market. The amount of epihalohydrin used is usually 4.0 to 10 mol, preferably 4.5 to 8.0 mol, and more preferably 5.0 to 7.0 mol per mol of hydroxyl group of AMSPN. During epoxidation, the produced epoxy resin and the phenolic hydroxyl group, which is an unreacted component, generally react to produce an epoxy resin having a glycerin ether moiety. It is preferable that the number of glycerin ether moieties is large because the toughness of the cured epoxy resin increases. On the other hand, if there are too many glycerin ether moieties, the increase in the molecular weight of the epoxy resin will increase the melt viscosity, resulting in a decrease in handling properties and an increase in the water absorption rate of the cured epoxy resin, which is undesirable, so the amount of epihalohydrin is used in accordance with the design. There is a need to. It is preferable to use epihalohydrin in excess of the hydroxyl groups of the raw material phenol resin because it is possible to suppress intermolecular reactions during epoxidation and to obtain an epoxy resin with low viscosity.

In the above reaction, an alkali metal hydroxide can be used as a catalyst to accelerate the epoxidation process. Examples of alkali metal hydroxides that can be used include sodium hydroxide, potassium hydroxide, etc., and solid forms or aqueous solutions thereof may be used; however, in the present invention, in particular, solubility, From the viewpoint of handling, it is preferable to use a solid material shaped into flakes.
The amount of alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1.15 mol per mol of hydroxyl group of AMSPN. It is a mole.

Further, in order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, etc. may be added as a catalyst. The amount of quaternary ammonium salt used is usually 0.1 to 15 mol, preferably 0.2 to 10 mol, per 1 mol of AMSPN hydroxyl group.

The reaction temperature is usually 30 to 90°C, preferably 35 to 80°C. Particularly in the present invention, the temperature is preferably 50°C or higher, particularly preferably 60°C or higher for higher purity epoxidation. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is too short, the reaction will not proceed to completion, and if the reaction time is too long, by-products will be produced, which is not preferable.
After washing the reactants of these epoxidation reactions with water, or without washing with water, epihalohydrin, solvent, etc. are removed under heating and reduced pressure. Furthermore, in order to obtain an epoxy resin with even less hydrolyzable halogen, the recovered epoxy resin is treated with a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent. It is also possible to ensure ring closure by dissolving the compound as a reaction mixture and adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to carry out the reaction. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of hydroxyl groups in AMSPN used for epoxidation. The reaction temperature is usually 50 to 120°C, and the reaction time is usually 0.5 to 2 hours.

After the reaction is completed, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of this embodiment.

Although the curable resin composition of this embodiment uses the epoxy resin of this embodiment as an essential component, other epoxy resins can also be used in combination without impairing the purpose of this embodiment. The epoxy resin may be liquid or solid, and may be used alone or in combination.

Examples of liquid epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, phenol novolac epoxy resin, and ester. Examples include alicyclic epoxy resins having a skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all made by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all made by Nippon Kayaku Co., Ltd.). manufactured by DIC Corporation, bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (manufactured by DIC Corporation, naphthalene type epoxy resin) , manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol novolac type epoxy resin) , "630", "630LSD" (manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), " "EX-721" (manufactured by Nagase ChemteX, glycidyl ester type epoxy resin), "Celoxide 2021P" (manufactured by Daicel, alicyclic epoxy resin with an ester skeleton), "PB-3600" (manufactured by Daicel, butadiene structure) ), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Examples of the solid epoxy resin include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, Biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin and biphenyl-type epoxy resins. Specific examples include "HP4032H" (manufactured by DIC, naphthalene type epoxy resin), "HP-4700", "HP-4710" (all of the above are naphthalene type tetrafunctional epoxy resins, manufactured by DIC), and "N-690". (manufactured by DIC Corporation, cresol novolak type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolak type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP- 7200'', ``HP-7200HH'', ``HP-7200H'' (manufactured by DIC, dicyclopentadiene type epoxy resin), ``EXA-7311'', ``EXA-7311-G3'', ``EXA-7311-G4'' , "EXA-7311-G4S", "HP-6000" (manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC -7000L", "NC-7300" (manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (The above are manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (the above, Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-" 4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin), "YX-8800" ( Mitsubishi Chemical Co., Ltd., anthracene type epoxy resin), "PG-100", "CG-500" (Osaka Gas Chemical Co., Ltd., fluorene type epoxy resin), "YL-7760" (Mitsubishi Chemical Co., Ltd., bisphenol AF type epoxy Resin), "YL-7800" (Mitsubishi Chemical Co., Ltd., fluorene type epoxy resin) "jER1010" (Mitsubishi Chemical Co., Ltd., solid bisphenol A type epoxy resin), "jER1031S" (Mitsubishi Chemical Co., Ltd., tetraphenylethane type) epoxy resin), etc. These may be used alone or in combination of two or more.

The amount of the epoxy resin blended may be within a range that does not impair the purpose of the present embodiment, but it is less than 50% by weight based on the total of AMSPNE and the resin. Preferably, AMSPNE is used in an amount of at least 60% by weight of the total epoxy resin, more preferably at least 75% by weight.

The epoxy resin of this embodiment can be used together with a known curing agent that can react with epoxy groups. Examples of the curing agent include phenol resins, amine resins, and active esters. The amount of curing agent used is preferably 0.8 to 1.5 equivalents per equivalent of epoxy groups in the epoxy resin. If the amount is less than 0.8 equivalents or more than 1.5 equivalents per equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

[Phenol resin]
A phenolic resin is a compound having two or more phenolic hydroxyl groups in its molecule. Examples of phenolic resins include reactants of phenols and aldehydes, reactants of phenols and diene compounds, reactants of phenols and ketones, reactants of phenols and substituted biphenyls, and phenols. Examples include, but are not limited to, reaction products of and substituted phenyls, and reaction products of bisphenols and aldehydes. Further, these may be used alone or in combination.
Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited thereto.
<Phenols>
Phenol, alkyl-substituted phenol, aromatic substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.
<Aldehydes>
Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.
<Diene compound>
Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.
<Ketones>
Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.
<Substituted biphenyls>
4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1' -Biphenyl etc.
<Substituted phenyls>
1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[Amine resin]
An amine resin is a compound having two or more amino groups in its molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, naphthalene diamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethyl. Aniline novolac (reaction product of orthoethylaniline and formalin), reaction product of 2-methylaniline and formalin, reaction product of 2,6-diisopropylaniline and formalin, reaction product of 2,6-diethylaniline and formalin, 2-ethyl - Reaction product of 6-ethylaniline and formalin, reaction product of 2,6-dimethylaniline and formalin, aniline resin obtained by reaction of aniline and xylylene chloride, substituted with aniline described in Japanese Patent No. 6429862 Reaction products of biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), aniline and substituted phenyls (1 , 4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylene) Examples include, but are not limited to, 4,4'-(1,4-phenylene diisopropylidene) bisaniline, a reaction product of aniline and diisopropenylbenzene, and dimer diamine. Further, these may be used alone or in combination.

[Active ester compound]
The active ester compound refers to a compound that contains at least one ester bond in its structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of active ester compounds include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. It can be obtained by a condensation reaction of at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to use a carboxylic acid compound or an acid chloride and a hydroxy compound, and as the hydroxy compound, a phenol compound or a naphthol compound is preferable. The active ester compounds may be used alone or in combination of two or more.

Examples of the carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecanedioyl dichloride, azeroyl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dichloride Examples include carbonyl chloride and 4,4'-azodibenzoyl dichloride.

Examples of the phenol compound and naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, Examples include phloroglucin, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak. Examples include ester compounds, the compound described in Example 2 of International Publication No. 2020/095829, and the compound disclosed in International Publication No. 2020/059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. The dicyclopentadiene type diphenol structure represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, containing an acetylated product of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester compound, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) is an acetylated product of phenol novolak as active ester compounds containing a benzoylated product of phenol novolac. Examples of the active ester curing agent include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the phosphorus atom-containing active ester curing agent include "EXB-9050L-62M" manufactured by DIC Corporation.

[Curing accelerator]
The curability of the curable resin composition of this embodiment can also be improved by adding a curing accelerator. The curing accelerator is preferably an anionic curing accelerator that accelerates the curing reaction by generating anions when heated, or a cationic curing accelerator that accelerates the curing reaction by generating cations when heated.

Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, and benzyl Examples include dimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine, 1,8-diazabicyclo(5 ,4,0)-undecene is preferred. Other examples include phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide, etc. It is not limited to these. Further, these may be used alone or in combination.

Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen, (Organic acid ions, hydroxide ions, etc., although there are no particular specifications, organic acid ions and hydroxide ions are particularly preferred.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen Examples include transition metal compounds (transition metal salts) such as zinc acid ester, zinc myristate), zinc phosphate ester (zinc octyl phosphate, zinc stearyl phosphate), but are not limited to these. Further, these may be used alone or in combination.

The amount of the curing accelerator used is 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

[Inorganic filler]
The curable resin composition of this embodiment may contain an inorganic filler. Examples of inorganic fillers include fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, Examples include, but are not limited to, powders such as steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, and inorganic fillers made of these in spherical or crushed shapes. It's not a thing. Further, these may be used alone or in combination.

The amount of inorganic filler used when obtaining a curable resin composition for semiconductor encapsulation is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, based on 100 parts by mass of the curable resin composition. be. In addition, when obtaining a curable resin composition for interlayer insulation layer forming material, copper clad laminate, prepreg, RCC, etc., the amount of the above-mentioned inorganic filler used is preferably 5% in the curable resin composition. ~80 parts by weight, more preferably 10 to 60 parts by weight.

[Polymerization initiator]
The curability of the curable resin composition of this embodiment can also be improved by adding a polymerization initiator. A polymerization initiator is a compound that can polymerize olefin functional groups such as ethylenically unsaturated bonds, and includes olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, radical polymerization initiators, etc. It will be done. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. A radical polymerization initiator is a compound that generates radicals upon heating and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacols. It is preferable to use

Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butyl peroxide). (oxyisopropyl)-dialkyl peroxides such as benzene, peroxyketals such as t-butylperoxybenzoate, 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t- Butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t -Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate Alkyl peresters such as oxybenzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butyl) Examples include, but are not limited to, peroxycarbonates such as peroxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. . Further, these may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, and dialkyl peroxides is more preferable.

Examples of the azo compounds include azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. However, it is not limited to these. Further, these may be used alone or in combination.

The amount of the polymerization initiator added is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, per 100 parts by weight of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, dielectric properties such as dielectric constant and dielectric loss tangent may be impaired.

[Polymerization inhibitor]
The curable resin composition of this embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, fluidity can be easily ensured, impregnating properties into glass cloth etc. are not impaired, and B-stage formation such as prepreg formation is facilitated. If the polymerization reaction progresses too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

The polymerization inhibitor may be added when synthesizing the epoxy resin of this embodiment, or may be added after synthesis. The amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the epoxy resin of this embodiment.

Examples of polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors. Furthermore, one kind of polymerization inhibitor may be used or a plurality of them may be used in combination. Among these, in the present invention, phenol type, hindered amine type, nitroso type, and nitroxyl radical type are preferable.

Examples of the phenolic polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio) Monophenols such as -6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol, 2 , 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t- butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1, 6-Hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy -hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy Benzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4, Bisphenols such as 8,10-tetraoxaspiro[5,5]undecane, bis(ethyl 3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium, 1,1,3-tris(2- Methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis- [Methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl) ) butyric acid] glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl Examples include, but are not limited to, polymeric phenols such as -4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione and tocophenol. .

Examples of the sulfur-based polymerization inhibitor include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like. However, it is not limited to these.

Examples of the phosphorus polymerization inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t -butylphenyl) phosphite, cyclic neopentanetetryrubis(octadecyl)phosphite, cyclic neopentanetetryruby(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetryruby(2, 4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, etc. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide, 10-desyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and other oxaphosphaphenanthrene oxides, etc. It is not limited.

Examples of the hindered amine polymerization inhibitor include Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Dekastab LA-82, Dekastab LA-81, Adekastab LA-77Y, and Adekastab LA-77Y. -77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, Tinuvi nPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB, etc. Examples include, but are not limited to.

Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine (cuperone), and the like. Among these, preferred is the ammonium salt of N-nitrosophenylhydroxyamine (cuperone).

Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6- Tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4- Methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6 Examples include, but are not limited to, -tetramethylpiperidine-1-oxyl and the like.

[Flame retardants]
The curable resin composition of this embodiment may contain a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), phosphorus-based flame retardants, etc., but halogen-free flame retardance has been achieved. From this viewpoint, phosphorus-based flame retardants are preferred.
The above-mentioned phosphorus-based flame retardant may be a reactive type flame retardant or an additive type flame retardant. Specific examples include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylenebis(dixylenyl phosphate), Phosphate esters such as 1,4-phenylenebis(dixylenyl phosphate) and 4,4'-biphenyl(dixylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- In addition to phosphanes such as oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, it is obtained by reacting an epoxy resin with the active hydrogen of the phosphanes. Examples include, but are not limited to, phosphorus-containing epoxy compounds, red phosphorus, and the like. Further, these may be used alone or in combination. Among the above-mentioned exemplified substances, phosphoric acid esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(dixylenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 4,4 '-Biphenyl (dixylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.

The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass, when the total nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. If it is less than 0.1 parts by mass, the flame retardance may be insufficient, and if it is more than 0.6 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[Light stabilizer]
A light stabilizer may be used in the curable resin composition of this embodiment. As the light stabilizer, hindered amine light stabilizers, particularly HALS, etc. are suitable. Examples of HALS include dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-( 2,2,6,6-tetramethyl-4-piperidyl)butylamine reaction product, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate reaction product , poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4- piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5 -bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2, 6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4- Examples include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate (hydroxybenzyl)-2-n-butylmalonate. It may be used in combination with two or more.

The content of the light stabilizer is preferably in the range of 0.001 to 10 parts by mass, when the total nonvolatile content excluding the inorganic filler in the curable resin composition is 100 parts by mass. If it is less than 0.001 parts by mass, it may be insufficient to exhibit a photostabilizing effect, and if it is more than 10 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[Binder resin]
The curable resin composition of this embodiment may use a binder resin. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, silicone resin, etc., but are not limited to these. It's not something you can do. Further, these may be used alone or in combination.

The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and the total nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. If so, the amount is preferably 0.05 to 50 parts by weight, more preferably 0.05 to 20 parts by weight.

[Additive]
The curable resin composition of this embodiment may use additives. Examples of additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, Examples include colorants such as phthalocyanine green.

The blending amount of the additive is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

The curable resin composition of the present embodiment further includes a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, a cyanate ester resin, a polybutadiene and a modified product thereof, a polystyrene and a modified product thereof. etc., and these may be used alone or in combination. Among these compounds, polyphenylene ether compounds, compounds with ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof may be included in view of the balance of heat resistance, adhesion, and dielectric properties. is preferred. By containing these compounds, the brittleness of the cured product can be improved and the adhesion to metal can be improved, and cracks in the package can be suppressed during reliability tests such as during solder reflow and cooling/heating cycles.

Unless otherwise specified, the amount of the compound used is preferably 10 times or less, more preferably 5 times or less, particularly preferably 3 times or less by mass, relative to the epoxy resin of this embodiment. . Further, a preferable lower limit is 0.1 times by mass or more, more preferably 0.25 times by mass or more, still more preferably 0.5 times by mass or more. By being within the above range, the effects of each compound added can be added while taking advantage of the effects of the epoxy resin of this embodiment. Regarding these components, those illustrated below can be used.

[Polyphenylene ether compound]
From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, methacrylic group, or styrene structure. preferable. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure).
The number average molecular weight (Mn) of the polyphenylene ether compound is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, and even more preferably from 2,000 to 4,000. If the molecular weight is less than 500, the cured product tends to have insufficient heat resistance. Furthermore, if the molecular weight is greater than 5,000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, which tends to result in poor molding. In addition, the reactivity decreases, and the curing reaction takes a long time, and unreacted substances increase without being incorporated into the curing system, lowering the glass transition temperature of the cured product and reducing the heat resistance of the cured product. There is a tendency to
When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, excellent heat resistance, moldability, etc. can be exhibited while maintaining excellent dielectric properties. Note that the number average molecular weight here can be specifically measured using gel permeation chromatography or the like.

The polyphenylene ether compound may be obtained by a polymerization reaction, or may be obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. Moreover, radical polymerizability may be imparted to these raw materials by reacting them with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by this redistribution reaction has hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain, and therefore can maintain even higher heat resistance. This is preferable because functional groups can be introduced at both ends of the molecular chain even after modification with a compound having a sexually unsaturated bond. Further, polyphenylene ether compounds obtained by polymerization reactions are preferred because they exhibit excellent fluidity.

In the case of a polyphenylene ether compound obtained by a polymerization reaction, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions and the like. Further, 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. More specifically, it may be possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the larger the amount of the phenolic compound blended, the lower the molecular weight of the resulting polyphenylene ether compound. At this time, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a polyfunctional phenol having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolak, cresol novolak, etc. type compounds are preferably used. These may be used alone or in combination of two or more.

The content of the polyphenylene ether compound is not particularly limited, but it may be 5 to 1000 parts by mass when the total mass of nonvolatile components excluding inorganic fillers in the curable resin composition is 100 parts by mass. The amount is preferably 10 to 750 parts by mass, and more preferably 10 to 750 parts by mass. When the content of the polyphenylene ether compound is within the above range, it is preferable that a cured product not only has excellent heat resistance but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[Compound containing an ethylenically unsaturated bond]
A compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in its molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.
Examples of compounds containing ethylenically unsaturated bonds include the above-mentioned phenolic resins and halogenated compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.) reactants, phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (1,4-bis( (chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy Examples include, but are not limited to, reaction products of resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.) and acid-modified products thereof. Further, these may be used alone or in combination.

[Isocyanate resin]
An isocyanate resin is a compound having two or more isocyanate groups in its molecule. Examples of the isocyanate resin include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate. , aromatic diisocyanates such as naphthalene diisocyanate, aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, isocyanate monomers Examples include, but are not limited to, polyisocyanates such as isocyanate bodies obtained by trimerizing one or more types of burettes or the above diisocyanate compounds, and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and a polyol compound. It's not a thing. Further, these may be used alone or in combination.

[Polyamide resin]
Examples of the polyamide resin include a reaction product of dicarboxylic acid with one or more of diamine, diisocyanate, and oxazoline, a reaction product of diamine and acid chloride, and a ring-opening polymer of a lactam compound. Further, these may be used alone or in combination.
Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited thereto.
<Diamine>
Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecane Diamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimer diamine, cyclohexanediamine, bis-(4- aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis( 4-Amino-3,5-dimethylphenyl)methanebis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-о-toluidine, 4,4'-methylenebis-о-ethylaniline, 4 , 4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenylsulfone, diaminodiphenyl ether, 1,3-bis( 3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4 '-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene , aminobenzylamine, diaminobenzophenone, etc.
<Diisocyanate>
Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2 -isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc.
<Dicarboxylic acid>
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4 , 4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc.
<Acid chloride>
Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacyl dichloride, adipic acid dichloride, dodecanedioyl dichloride, azeloyl chloride, 2, 5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl)ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azo Dibenzoyl dichloride etc.
<Lactam>
ε-caprolactam, ω-undecanelactam, ω-laurolactam, etc.

[Polyimide resin]
Examples of polyimide resins include, but are not limited to, reaction products of the diamines described above and tetracarboxylic dianhydrides exemplified below. Further, these may be used alone or in combination.
<Tetracarboxylic dianhydride>
4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic acid dianhydride Anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride Acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3 '-Biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4 '-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4 , 4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride Anhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1 , 4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4- (3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3 ,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3 , 3-tetramethyldisiloxane dianhydride, 2,3,6,7-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-phenanthrene Tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), cyclopentane Tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4' -Bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[ 2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic 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-tetrahydro Naphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl)ether, 4,4'-biphenylbis(trimellitic acid monoester acid anhydride), 9,9 '-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[Cyanate ester resin]
Cyanate ester resin is a compound obtained by reacting a phenol resin with cyanogen halide, and 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, Examples include, but are not limited to, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and a phenol/dicyclopentadiene cocondensate with the hydroxyl group converted to a cyanate group. Further, these may be used alone or in combination.
Furthermore, cyanate ester compounds whose synthesis method is described in JP-A No. 2005-264154 are particularly preferred as cyanate ester compounds because they have low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
The cyanate ester resin can optionally trimerize cyanate groups to form a sym-triazine ring. Catalysts such as lead acetylacetonate and dibutyltin maleate can also be included.

The catalyst is 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0, based on 100 parts by mass of the total mass of nonvolatile components excluding the cyanate ester resin and inorganic filler in the curable resin composition. .0015 parts by mass is used.

[Polybutadiene and its modified products]
Polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. In the structure derived from polybutadiene, some or all of the unsaturated bonds may be converted into single bonds by hydrogenation.
Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl group-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, etc. . Further, these may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Clay Valley), and 1,2-SBS (manufactured by Nippon Soda), and examples of polybutadiene include: Examples include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The weight average molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during preparation of prepreg, and above the upper limit of the above range, compatibility with other curable resins deteriorates. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, due to their polarity, compounds consisting mainly of hydrocarbons or compounds consisting only of hydrocarbons have low polarity. It is difficult to ensure compatibility with other compounds. On the other hand, the epoxy resin of this embodiment does not have a skeleton design that actively introduces heteroatoms such as oxygen or nitrogen, and is made of materials with low polarity and low dielectric properties, or only hydrocarbons. It also has excellent compatibility with the constituent compounds.

[Polystyrene and its modified products]
Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the molecule.
Examples of polystyrene and its modified products include polystyrene, styrene/2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), and SEP (styrene-ethylene/propylene copolymer). Polymer: SEPTON 1020 manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene propylene-styrene copolymer: SEPTON 2002, SEPTON 2004F, SEPTON 2005, SEPTON 2006, SEPTON 2063, SEPTON 2104 manufactured by Kuraray Co., Ltd.), SEEPS (Styrene - Ethylene/ethylene propylene-styrene block copolymer: SEPTON 4003, SEPTON 4044, SEPTON 4055, SEPTON 4077, SEPTON 4099 (all manufactured by Kuraray), SEBS (styrene-ethylene/butylene-styrene block copolymer: SEPTON 8004) , SEPTON 8006, SEPTON 8007L (all manufactured by Kuraray), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene/ethylene propylene-styrene block copolymer: SEPTON HG252 manufactured by Kuraray), SIS (styrene-isoprene) -Styrene block copolymers: SEPTON 5125, SEPTON 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: HYBRAR 7125F, HYBRAR 7311F, both manufactured by Kuraray Co., Ltd.), SIBS (styrene -Isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka), Septon V9827 (manufactured by Kuraray), etc., but are not limited to these. Further, these may be used alone or in combination. Polystyrene and its modified products have higher heat resistance and are less susceptible to oxidative deterioration, so polystyrenes that do not have unsaturated bonds are preferred. The weight average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, in addition to polyphenylene ether compounds, low molecular weight components with weight average molecular weights of about 50 to 1,000 and weight average molecular weights of 1,000 to 1,000 are used. The molecular weight is preferably about 10,000 to 300,000, since the compatibility with oligomer components of about 5,000 will deteriorate and it will be difficult to ensure mixing and solvent stability.

The method for preparing the curable resin composition of this embodiment is not particularly limited, but the components may be simply mixed uniformly or may be prepolymerized. For example, it is prepolymerized by heating in the presence or absence of the epoxy resin of this embodiment, a curing agent, a curing accelerator, and a polymerization initiator, and in the presence or absence of a solvent. Similarly, compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, inorganic fillers, and other additives are added to preform. It may also be made into a polymer. For mixing or prepolymerization of each component, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reaction vessel equipped with a stirring device, etc., is used in the presence of a solvent.

The method for uniformly mixing is to knead the resin composition using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100° C. to obtain a uniform resin composition. After the obtained resin composition is crushed, it is molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or it is made into a granular powder or powder-like molded product, or the composition is molded onto a surface support. It is also possible to make a curable resin composition molded product by melting it and molding it into a sheet with a thickness of 0.05 mm to 10 mm. The obtained molded product becomes a non-sticky molded product at 0 to 20°C, and its fluidity and hardenability hardly decrease even if it is stored at -25 to 0°C for one week or more.
The obtained molded product can be molded into a cured product using a transfer molding machine or a compression molding machine.

The curable resin composition of this embodiment can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, etc. as necessary to form a varnish, which can be applied to glass fibers or carbon. A cured product of the curable resin composition of this embodiment is obtained by hot press molding a prepreg obtained by impregnating a base material such as fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. I can do it. The solvent used in this case is used in an amount that accounts for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present embodiment and the solvent. Further, if the composition is a liquid composition, a cured resin containing carbon fibers can be obtained as it is, for example, by the RTM method.

A semiconductor device can be manufactured using the curable resin composition of this embodiment. Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), and TQFP. (Think Quad Flat Package), etc.

The curable resin composition of this embodiment and its cured product can be used in a wide range of fields. Specifically, it can be used for various purposes such as molding materials, adhesives, composite materials, and paints. Since the cured product of the curable resin composition according to the present invention exhibits excellent heat resistance and dielectric properties, it can be used as an encapsulant for semiconductor devices, an encapsulant for liquid crystal display devices, an encapsulant for organic EL devices, a laminate ( It is suitably used for electrical/electronic parts such as printed wiring boards, BGA substrates, build-up boards, etc., composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

The present invention will be explained in more detail with reference to synthesis examples and examples below. The materials, processing details, processing procedures, etc. shown below can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.

Various analytical methods were conducted under the following conditions.
-Epoxy equivalent Measured by the method described in JIS K-7236, and the unit is g/eq. It is.
- Softening point Measured according to JIS K-7234, and the unit is °C.
- Melt viscosity ICI melt viscosity (150° C.) Measured by cone plate method, unit is Pa·s.

・Hydroxyl group equivalent Measured by the following method, and the unit is g/eq. It is.
The phenolic resin is reacted with excess acetic anhydride and titrated with 0.5N KOH ethanol solution using a potentiometer to measure the amount of free acetic acid.
Reagent: acetic anhydride, triphenylphosphine, pyridine Solvent: tetrahydrofuran, propylene glycol monomethyl ether Automatic titrator: COM-1600 manufactured by HIRANUMA Co., Ltd.
Bullet: B-2000 manufactured by HIRANUMA Co., Ltd.

・GPC (gel permeation chromatography) analysis Manufacturer: Shimadzu Column: Guard column KF-G4A GPC KF-601 (1 piece), KF-602 KF-602.5, KF-603
Flow rate: 1.5ml/min.
Column temperature: 40℃
Solvent used: THF (tetrahydrofuran)
Detector: RID-20A (differential refraction detector)

・LC-MS analyzer: Q-Exactive (Thermo Fisher Scientific)
Column: CORTECS C18 2.1 x 150mm (2.7μm)
Oven: 40℃
MobilPhaseA: 5mM ammonium acetate aqueous solution MobilPhaseB: Acetonitrile TimeProgram:
50%-20min-99%-10min-99%
FlowRate: 0.3mL/min.
Detection: PDA (190-800nm), FT-MS (m/z=50-750, 100-1500)

・^1H -NMR analyzer: JNM-ECS400 manufactured by JEOL Ltd.

[Example 1]
Into a flask equipped with a stirrer, a reflux condenser, and a stirring device, 310 g of phenol novolak (hydroxyl equivalent: 103.5), 15.9 g of toluene, and 1.65 g of p-toluenesulfonic acid as an acid catalyst were charged, stirred, and dissolved. After heating to 100° C., 118 g of α-methylstyrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 3 hours. Thereafter, the mixture was reacted at 100°C for 9 hours. The mixture was then cooled to room temperature, dissolved in 800 g of toluene, and neutralized by adding 0.15 g of sodium carbonate and 190 g of water. After repeated washing with water, toluene and unreacted phenol were distilled off under heating and reduced pressure to form a hydroxy resin represented by the following formula (2A) (R ₂ is a substituent represented by the following formula (2A-a)). , p _ave was 0.57, n _ave was 7.7, and q _ave was 0.02). Its hydroxyl equivalent is 168.9g/eq. The softening point was 84°C, and the melt viscosity at 150°C was 1.10 Pa·s. The GPC chart is shown in Figure 1, the LC-MS chart is shown in Figure 2, and ^{the 1H} -NMR chart (400MHz, DMSO-d) is shown in Figure 3. The number average molecular weight (Mn) was 1301.

(In formula (2A-a), the wavy line indicates the binding site.)

In the LC-MS chart of FIG. 2, for example, the peak at 11.85 minutes is a compound with a molecular weight of n=1 and two α-methylstyrenes, and the following formula (5), formula (6), formula ( There are three possible structures represented by 7).

[Example 2]
For 478 g of the phenolic resin obtained in Example 1, 1252 g of epichlorohydrin (ECH, the same hereinafter), 228 g of dimethyl sulfoxide (DMSO, the same hereinafter), and 46 g of water were charged into a reaction vessel, and after heating, stirring, and dissolution, flaky 5.0 g of sodium hydroxide was charged at once, and the reaction was carried out at 55° C. for 1.5 hours. Thereafter, while maintaining the temperature at 55° C., 101.9 g of flaky sodium hydroxide was charged in portions over 90 minutes. Thereafter, the reaction was carried out at 55°C for 90 minutes and at 70°C for 60 minutes. Excess epichlorohydrin was then distilled off from the oil layer under heating and reduced pressure, and 1232 g of methyl isobutyl ketone was added to the residue and dissolved, followed by washing with water to remove by-product salts and dimethyl sulfoxide. This methyl isobutyl ketone solution was heated to 75° C., 32.8 g of a 30% aqueous sodium hydroxide solution was added, and after reacting for 1 hour, washing of the reaction solution with water was repeated until the washing solution became neutral. Then, methyl isobutyl ketone is distilled off from the oil layer under heating and reduced pressure to obtain an epoxy resin represented by the following formula (1A) (R ₂ is a substituent represented by the following formula (1A-a), p _ave , n _ave , q _ave are the same as in Example 1). The GPC chart is shown in FIG. 4, and the LC-MS chart is shown in FIG. 5. The number average molecular weight (Mn) was 1402.

(In formula (1A), G represents a glycidyl group.)

(In formula (1A-a), the wavy line indicates the binding site.)

[Example 3]
Into a flask equipped with a stirrer, a reflux condenser, and a stirring device, 103.5 g of phenol novolak (hydroxyl equivalent: 103.5), 5.30 g of toluene, and 0.55 g of p-toluenesulfonic acid as an acid catalyst were charged, stirred, and dissolved. Thereafter, 118.50 g of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise to the mixture heated to 100° C. over 3 hours. Thereafter, the mixture was reacted at 100° C. for 14 hours. The mixture was then cooled to room temperature, dissolved in 330 g of toluene, and neutralized by adding 0.05 g of sodium carbonate and 100 g of warm water. After repeated washing with water, toluene and unreacted phenol were distilled off under heating and reduced pressure to form a compound represented by the following formula (2B) (R ₂ is a substituent represented by the following formula (2B-a), p _ave was 0.48, n _ave was 7.7, and q _ave was 1.39). Its hydroxyl equivalent is 257.7g/eq. Met. The GPC chart is shown in FIG. 6, and ^{the 1} H-NMR chart (400 MHz, DMSO-d) is shown in FIG. 7. The number average molecular weight (Mn) was 675.

(In formula (2B-a), the wavy line indicates the binding site.)

[Example 4]
For 185 g of the phenolic resin obtained in Example 3, 366.3 g of epichlorohydrin (ECH, the same below), 66.6 g of dimethyl sulfoxide (DMSO, the same below), and 13.32 g of water were charged into a reaction vessel, heated, stirred, After dissolving, 1.5 g of flaky sodium hydroxide was added at once, and the reaction was carried out at 55° C. for 1.5 hours. Thereafter, while maintaining the temperature at 55° C., 29.8 g of flaky sodium hydroxide was charged in portions over 90 minutes. Thereafter, the reaction was carried out at 55°C for 90 minutes and at 70°C for 60 minutes. Excess epichlorohydrin was then distilled off from the oil layer under heating and reduced pressure, and 452 g of methyl isobutyl ketone was added to the residue and dissolved, followed by washing with water to remove by-product salts and dimethyl sulfoxide. This methyl isobutyl ketone solution was heated to 75° C., 9.6 g of a 30% aqueous sodium hydroxide solution was added, and after reacting for 1 hour, washing of the reaction solution with water was repeated until the washing solution became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure. The obtained solid resin was dissolved in 80 g of toluene and purified by reprecipitation twice with MeOH to obtain an epoxy resin represented by the following formula (1B) (R ₂ is represented by the following formula (1B-a)). The substituents p _ave , n _ave , and q _ave are the same as in Example 3.) was obtained. The GPC chart is shown in FIG. The number average molecular weight (Mn) was 1133.

(In formula (1B), G represents a glycidyl group.)

(In formula (1B-a), the wavy line indicates the binding site.)

Epoxy resin obtained in Examples 2 and 4, phenol novolac type epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resin (EOCN-1020-55, manufactured by Nippon Kayaku Co., Ltd.), styrene modification Table 1 shows the properties of the phenol novolac type epoxy resin (synthesized with reference to Comparative Example 2 in Patent No. 6406847).

[Examples 5 and 6, Comparative Examples 1 to 3]
Various epoxy resins, phenol novolac (H-1 manufactured by Nippon Kayaku Co., Ltd.) as a curing agent, and triphenylphosphine (TPP manufactured by Hokko Chemical Co., Ltd.) as a curing accelerator were mixed in the weight ratio shown in Table 2.

<Water absorption test>
The curable resin compositions of Examples 5 and 6 and Comparative Examples 1 to 3 were cured at 160°C for 2 hours and at 180°C for 6 hours to produce cured products. A disk-shaped test piece with a diameter of 5 cm and a thickness of 4 mm was boiled in water at 100° C. for 24 hours, and the weight increase rate (%) from the initial value was measured. The results are listed in Table 3.

<DMA measurement>
Cured products of the curable resin compositions of Example 5 and Comparative Examples 1 to 3 were prepared under curing conditions of 160°C for 2 hours and 180°C for 6 hours. DMA measurement was performed under the following conditions, and the results are shown in Table 4 and FIG. 9.
Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measurement temperature range: 25-280℃
Heating rate: 2°C/min Measurement mode: Tension Heating rate: 2°C/min.
Measurement frequency: 10Hz

From the results in Table 3, it was confirmed that Examples 5 and 6 were excellent in low water absorption. Further, from the results shown in Table 4 and FIG. 9, it was confirmed that Example 5 had high elasticity in the practical use temperature range (30°C, 100°C) and low elasticity at high temperature (260°C).

[Examples 7 and 8, Comparative Example 4]
Various epoxy resins and a curing agent (biphenylaralkyl phenol resin, MEHC-7800SS manufactured by Meiwa Kasei Co., Ltd.) were mixed in equal amounts, and triphenylphosphine (TPP manufactured by Hokko Chemical Co., Ltd.) was added as a curing accelerator at 2% by weight based on the epoxy resin. , filler (fused silica, MSR-2122 manufactured by Takimori) was added in an amount of 83% by weight based on the entire curable resin composition, and mixed and kneaded uniformly using a mixing roll to form a curable resin composition. Obtained. This curable resin composition was pulverized using a mixer, and then tableted using a tablet machine. This tabletted curable resin composition was transfer molded (175°C x 60 seconds), and after demolding, a test piece for curing evaluation was obtained under the conditions of 160°C x 2 hours + 180°C x 6 hours. A flame retardancy test was conducted under the following conditions, and the results are listed in Table 5.

<Flame retardancy test>
- Judgment of flame retardancy: Conducted in accordance with UL94. However, the sample size was 12.5 mm wide x 150 mm long, and the test was conducted with a thickness of 0.8 mm.
・Afterflame time: Total afterflame time after applying flame to a set of 5 samples 10 times

From the results in Table 5, it was confirmed that Examples 7 and 8 were excellent in flame retardancy.

Claims (8)

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

(In formula (1), G represents a glycidyl group. Plural R ₁ 's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Plural R ₂ 's are represented by the following formula (1 Indicates a substituent represented by -a).The plural ps are each a real number from 0 to 3, and the average p _ave is 0.1≦p _ave ≦3.0.n is the number of repetitions. and the average value n _ave of n is 1≦n _ave ≦20.)

(In formula (1-a), a plurality of R _3s exist independently and represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0.01≦q _ave ≦3. The wavy line indicates the binding site.) Epoxy equivalent is 265g/eq. More than 320g/eq. The epoxy resin according to claim 1, which is as follows. The epoxy resin according to claim 1, having a softening point of 50°C or more and 90°C or less. A curable resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing agent. The curable resin composition according to claim 4, further comprising a curing accelerator. A cured product obtained by curing the curable resin composition according to claim 4. A semiconductor sealing material obtained by curing the curable resin composition according to claim 4. A polyhydric hydroxy resin represented by the following formula (2).

(In formula (2), multiple R ₁ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and multiple R ₂ 's are substituted by the following formula (2-a). The plurality of ps are each a real number from 0 to 3, and the average value p _ave of p is 0.1≦p _ave ≦3.0. n is the number of repetitions, and the average value n of n _ave is 1≦n _ave ≦20.)

(In formula (2-a), a plurality of R ₃ 's each independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. q is the repeating number, and the average value q _ave of q is 0. 01≦q _ave ≦3. The wavy line indicates the binding site.)

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