Curable resin composition, cured product, and electric / electronic part

Abstract

To provide a curable resin composition that excels in heat resistance, low elastic properties, and low dielectric constant properties.SOLUTION: The foregoing problem can be solved by a curable resin composition that comprises an epoxy compound (A) represented by the formula (1), an epoxy compound (B) represented by the formula (2) and an active ester-based curing agent (C).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition, and further relates to a cured product obtained by curing the curable resin composition, an electric / electronic component, and a laminate, as well as an encapsulant containing the curable resin composition. [Background technology]

[0002] In recent years, the importance of thermosetting resins used as semiconductor materials has been increasing along with the high level of electronic equipment in automobiles. In particular, the components surrounding automobile engines are exposed to high temperatures for long periods of time and high voltages are applied, so they require high heat resistance, high strength, and high insulation reliability.

[0003] One method of imparting high heat resistance to a thermosetting resin is to increase the glass transition temperature. Another method of imparting high strength is to reduce the elastic modulus of the thermosetting resin to facilitate stress relaxation. Another method of imparting high insulation reliability is to reduce the dielectric constant.

[0004] Among thermosetting resins, epoxy resins are known to be highly reliable semiconductor materials. There are many curing agents that can be combined with epoxy resins, and their functions can be adjusted by combining them according to the purpose. Furthermore, by combining multiple epoxy resins, it is possible to impart advanced functions that cannot be achieved with a single epoxy resin.

[0005] Patent Document 1 describes a resin composition for an insulating layer of a multilayer printed wiring board, which contains an epoxy resin having a xylene structure, a curing agent, and an inorganic filler, and further describes the use of an active ester curing agent as the curing agent. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2014-36172 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the resin composition characterized by containing an epoxy resin having a xylene structure and an active ester-based curing agent described in Patent Document 1 was not satisfactory in terms of low elastic modulus, high heat resistance, and low dielectric constant for automotive semiconductor applications. In view of the above problems, an object of the present invention is to provide a curable resin composition excellent in heat resistance, low elasticity characteristics, and low dielectric constant characteristics. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by a curable resin composition comprising an epoxy resin having a xylene structure, an epoxy resin having a tetramethylbiphenyl structure, and an active ester-based curing agent. That is, the gist of the present invention resides in the following [1] to

[11] .

[0009] [1] A curable resin composition comprising an epoxy compound (A) represented by the following formula (1), an epoxy compound (B) represented by the following formula (2), and an active ester-based curing agent (C). [ka] (In the above formula (1), m is the average number of repetitions and is 0 or more, and n is the average number of repetitions and is greater than 0.) [ka] [2] The curable resin composition according to [1], wherein the content of the epoxy compound (B) is 1 to 999 parts by weight based on 100 parts by weight of the epoxy compound (A). [3] The curable resin composition according to [1] or [2], wherein the content of hydrolyzable halogen in the epoxy compound (A) is 1000 ppm by weight or less. [4] The curable resin composition according to any one of [1] to [3], wherein the content of the active ester-based curing agent (C) is 1 to 500 parts by weight per 100 parts by weight of the total content of the epoxy compound (A) and the epoxy compound (B). [5] The curable resin composition according to any one of [1] to [4], further comprising a curing agent (E) other than the active ester-based curing agent (C), wherein the content of the curing agent (E) is 0.01 to 1000 parts by weight per 100 parts by weight of the total content of the epoxy compound (A), the epoxy compound (B) and the active ester-based curing agent (C) in the curable resin composition. [6] The curable resin composition according to [5], wherein the curing agent (E) comprises at least one selected from the group consisting of a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, an amide-based curing agent, and a radical polymerizable resin. [7] The curable resin composition according to [6], wherein the radical polymerizable resin contains at least one substituent selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a butadiene group. [8] A cured product obtained by curing the curable resin composition according to any one of [1] to [7]. [9] An electric / electronic part obtained by curing the curable resin composition according to any one of [1] to [7].

[10] A laminate obtained by curing the curable resin composition according to any one of [1] to [7].

[11] An encapsulant comprising the curable resin composition according to any one of [1] to [7]. Effect of the Invention

[0010] According to the present invention, it is possible to provide a curable resin composition having excellent heat resistance, low elasticity and low dielectric constant properties, as well as a cured product, an electric / electronic component, a laminate and an encapsulant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following is a detailed description of an embodiment of the present invention, but the description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. Note that when the expression "~" is used in this specification, it is used as an expression including the numerical values ​​or physical property values ​​before and after it. The epoxy resin of the present embodiment may be either one containing a repeating structure or one having a monomolecular structure, but in the art, any epoxy compound may be expressed and sold as an "epoxy resin" or an "epoxy resin composition." In addition, in the art, a mixture further containing an epoxy resin different from the epoxy resin of the present embodiment may be expressed as an "epoxy resin composition," or may simply be called an "epoxy resin."

[0012] [Curable resin composition] A curable resin composition according to one embodiment of the present invention contains an epoxy compound (A) represented by the following formula (1), an epoxy compound (B) represented by the following formula (2), and an active ester-based curing agent (C). [ka]

[0013] (In the above formula (1), m is the average number of repetitions and is 0 or more, and n is the average number of repetitions and is greater than 0.) [ka]

[0014] <Epoxy compound (A)>

[0015] The curable resin composition of the present embodiment contains an epoxy compound (A) (hereinafter sometimes simply referred to as epoxy compound (A)) represented by the following formula (1). [ka]

[0016] In the above formula (1), m is the average number of repetitions and is 0 or more, and n is the average number of repetitions. m is an average value and is greater than 0. From the viewpoint of keeping the viscosity of the epoxy resin low and the softening point at or above a certain temperature, m is preferably 0 or more and 10 or less, more preferably 0 or more and 8 or less, and even more preferably 0 or more and 6 or less. From the same viewpoint, n is preferably greater than 0 and 10 or less, more preferably greater than 0 and 8 or less, particularly preferably greater than 0 and 6 or less, and most preferably 1 or more and 6 or less.

[0017] The epoxy compound (A) represented by the above formula (1) can be obtained by reacting a phenol compound represented by the following formula (3) with epihalohydrin. [ka]

[0018] In the above formula (3), m is the average number of repetitions and is 0 or more, and n is the average number of repetitions and is greater than 0. The preferred ranges of m and n are the same as those in the above formula (1).

[0019] The quality properties of the epoxy compound (A) obtained by the reaction of the above formula (3) with epihalohydrin vary depending on the type and use ratio of each component, but it is preferable to adjust various conditions so that the epoxy equivalent is usually 150 to 330 g / eq., preferably 180 to 300 g / eq., and more preferably 200 to 290 g / eq., the melt viscosity at 150°C is usually 0.9 Pa·s or less, preferably 0.7 Pa·s or less, and more preferably 0.5 Pa·s or less, the softening point is usually 50 to 120°C, preferably 60 to 110°C, and more preferably 62 to 100°C, the hydrolyzable halogen is usually 1000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less, and the volatile content (including water) is usually 0.9 mass% or less, preferably 0.6 mass% or less, and more preferably 0.3 mass% or less.

[0020] If the epoxy equivalent is too small, the moisture absorption will be poor, and if it is too large, the curing will be impaired. If the melt viscosity is too high, the flowability during molding will be impaired. If the softening point is too low, it will be difficult to handle as a solid, and if it is too high, it will be difficult to mix with phenolic resins, etc. If there is too much hydrolyzable halogen, there is a possibility that halogen ions in the encapsulant will cause defects due to corrosion of the aluminum wiring of semiconductor integrated circuits. If there is a large amount of volatile components, there is a possibility that curing will be poor and it will also lead to a deterioration of the working environment when handling at high temperatures.

[0021] The method for producing the phenol compound represented by the above formula (3) may, for example, be a method of reacting an aromatic hydrocarbon formaldehyde resin with a phenol in the presence of an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid, or an acidic catalyst such as toluenesulfonic acid, xylenesulfonic acid, or oxalic acid, and then reacting the resulting mixture with formaldehyde using the acidic catalyst or a neutral catalyst such as calcium acetate, magnesium acetate, zinc acetate, other organic acid metal salts, or zinc oxide. Alternatively, the method may be a method of reacting a phenol with formaldehyde, and then reacting the resulting mixture with an aromatic hydrocarbon formaldehyde, or a method of simultaneously reacting an aromatic hydrocarbon formaldehyde resin, a phenol, and formaldehyde.

[0022] The compound represented by the above formula (3) thus obtained has a hydroxyl equivalent of 100 to 270 g / eq., preferably 120 to 240 g / eq., and more preferably 140 to 220 g / eq., a melt viscosity at 150°C of 1.1 Pa s or less, preferably 0.9 Pa s or less, and more preferably 0.7 Pa s or less, a softening point of 70 to 160°C, preferably 80 to 180°C, and more preferably 100 to 240 g / eq., and more preferably 100 to 220 g / eq., and a melt viscosity at 150°C of 1.1 Pa s or less, preferably 0.9 Pa s or less, and more preferably 0.7 Pa s or less, and a softening point of 70 to 160°C, preferably 80 to 180°C. It is preferable to adjust various conditions so that the temperature is 0 to 130°C, more preferably 80 to 100°C.

[0023] The amount of free phenol contained in the phenolic resin of the above formula (3) is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. If the amount of free phenol is too much, not only will the heat resistance of the cured product of the epoxy resin composition decrease, but the working environment will also deteriorate when the epoxy resin composition is handled at high temperatures. The hydroxyl equivalent was measured according to JIS K0070, the softening point according to JIS K7234, and the free phenol content according to the GC method.

[0024] The epoxy compound (A) obtained by the reaction of the compound represented by the above formula (3) with epihalohydrin can be produced by a known method. A typical example is described in detail below. First, 3 to 20 moles of epihalohydrin is dissolved per mole of phenolic hydroxyl group to obtain a homogeneous solution. Next, while stirring the solution, 0.9 to 2.0 moles of alkali metal hydroxide per mole of phenolic hydroxyl group is added as a solid or aqueous solution to react. This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is usually 30 to 150°C in the case of a reaction under normal pressure, and 30 to 80°C in the case of a reaction under reduced pressure. The reaction is dehydrated by azeotroping the reaction liquid while maintaining a predetermined temperature as necessary, cooling the volatilized steam to obtain a condensate, separating the oil and water, and returning the oil with the moisture removed to the reaction system. The alkali metal hydroxide is added intermittently or continuously in small amounts over 1 to 8 hours to suppress a rapid reaction. The total reaction time is usually 1 to 10 hours.

[0025] After the reaction is completed, the insoluble by-product salt is removed by filtration or by washing with water, and the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin. As the epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used. As the alkali metal hydroxide, sodium hydroxide or potassium hydroxide is usually used.

[0026] In addition, in this reaction, a catalyst such as a quaternary ammonium salt such as tetramethylammonium chloride or tetraethylammonium bromide; a tertiary amine such as benzyldimethylamine or 2,4,6-tris(dimethylaminomethyl)phenol; an imidazole such as 2-ethyl-4-methylimidazole or 2-phenylimidazole; a phosphonium salt such as ethyltriphenylphosphonium iodide; or a phosphine such as triphenylphosphine may be used.

[0027] Furthermore, in this reaction, inert organic solvents such as alcohols such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; and aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide may be used.

[0028] Furthermore, if the epoxy resin obtained as described above has too much saponifiable halogen, it can be reprocessed to obtain a purified epoxy resin with a sufficiently reduced amount of saponifiable halogen. That is, the crude epoxy resin is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, or dimethyl sulfoxide, and an alkali metal hydroxide is added as a solid or aqueous solution to carry out a ring-closing reaction at a temperature of about 30 to 120°C for 0.5 to 8 hours. Then, the excess alkali metal hydroxide or secondary salt is removed by a method such as washing with water, and the organic solvent is removed by distillation under reduced pressure to obtain a purified epoxy resin.

[0029] Furthermore, it is preferable to adjust various conditions so that the epoxy equivalent is 1.00 to 1.50 times, preferably 1.00 to 1.20 times, the theoretical value calculated from the hydroxyl equivalent of the phenolic resin of the above formula (3). The theoretical value here is the value when all the hydroxyl groups of the phenolic resin of general formula (1) are glycidylated, and if the epoxy equivalent is too large than the theoretical value, it is considered that the hydroxyl groups have reacted with something other than epihalohydrin, resulting in polymerization, etc., and there is concern about deterioration of curability and the presence of impurities.

[0030] <Epoxy compound (B)> The curable resin composition of the present embodiment contains an epoxy compound (B) (hereinafter sometimes simply referred to as epoxy compound (B)) represented by the following formula (2). [ka]

[0031] The epoxy compound (B) represented by the above formula (2) (hereinafter, may be simply referred to as epoxy compound (B)) can be obtained by reacting a phenol compound represented by the following formula (4) with epihalohydrin. [ka]

[0032] The quality properties of the epoxy compound (B) obtained by the reaction of the above formula (4) with epihalohydrin vary depending on the type and use ratio of each component, but it is preferable to adjust various conditions so that the epoxy equivalent is usually 170 to 300 g / eq., preferably 175 to 250 g / eq., and more preferably 180 to 230 g / eq., the melt viscosity at 150°C is usually 0.1 Pa·s or less, preferably 0.05 Pa·s or less, and more preferably 0.03 Pa·s or less, the melting point is usually 60 to 130°C, preferably 70 to 120°C, and more preferably 80 to 110°C, the hydrolyzable halogen is usually 1000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less, and the volatile content (including water) is usually 0.9 mass% or less, preferably 0.6 mass% or less, and more preferably 0.3 mass% or less.

[0033] If the epoxy equivalent is too low, the moisture absorption will be poor, and if it is too high, the curing will be poor. If the melt viscosity is too high, the flowability during molding will be impaired. If the melting point is too low, it will be difficult to handle as a powder, and if it is too high, it will be difficult to mix with phenolic resins, etc. If there is too much hydrolyzable halogen, there is a possibility that halogen ions in the encapsulant will cause defects due to corrosion of the aluminum wiring of semiconductor integrated circuits. If there is a lot of volatile components, there is a possibility that curing will be poor and at the same time, it will also lead to a deterioration of the working environment when handling at high temperatures.

[0034] Considering the quality properties of the compound represented by the above formula (4) after subsequent epoxidization, it is preferable to adjust various conditions so that the hydroxyl group equivalent is usually 100 to 1800 g / eq., preferably 110 to 160 g / eq., and more preferably 115 to 140 g / e, although this varies depending on the type and use ratio of each component.

[0035] The epoxy resin (B) obtained by reacting the compound represented by the above formula (4) with epihalohydrin can be produced by a known method, and the preferred range is the same as that of the epoxy resin (A) obtained by reacting the compound represented by the above formula (3) with epihalohydrin.

[0036] <Active ester curing agent (C)> The curable resin composition of the present embodiment contains an active ester-based curing agent (C) from the viewpoint of imparting low water absorption and low dielectric properties to the resulting cured product.

[0037] The active ester curing agent (C) is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used.

[0038] The active ester curing agent (C) is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance in particular, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred.

[0039] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phloroglucin, benzenetriol, and dicyclopentadiene-phenol addition type resin.

[0040] Specific examples of the active ester curing agent (C) that are preferred include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins which are acetylated phenol novolac, and active ester resins which are benzoylated phenol novolac. Among these, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in terms of their excellent ability to improve peel strength.

[0041] More specifically, the active ester resin containing a dicyclopentadiene-phenol adduct structure includes compounds represented by the following general formulas (I) and (II).

[0042] [ka]

[0043] In the above formula (I), B' is independently any structural moiety selected from the group consisting of the following structural formulae (B'-1) to (B'-6), R 21 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; Z represents a phenyl group, a naphthyl group, or a phenyl group or naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus; l is 0 or 1; and k' is an average of 0.05 to 3.5 for the repeating units. [ka]

[0044] In the above formulas (B'-1) to (B'-6), R 22 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group; R 23each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; Y represents a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group; and o and p are integers of 1 to 4.

[0045] [ka]

[0046] In formula (II), W is a phenyl group or a naphthyl group, l' represents 0 or 1, and k'' is an average of the repeating units of 0.05 to 3.5. In formula (II), from the viewpoints of decreasing the dielectric tangent and improving the heat resistance of the cured product of the resin composition, R is preferably a naphthyl group, l' is preferably 0, and k'' is preferably 0.25 to 1.5. Moreover, polyarylates can also be used as hardeners similar to the active ester resins represented by the general formulas (I) and (II).

[0047] As the active ester curing agent (C) of this embodiment, a commercially available active ester compound may be used. Commercially available active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation), active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation), active ester compounds which are acetylated phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation), and active ester curing agents which are benzoylated phenol novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0048] The active ester curing agent (C) listed above may be used alone or in any combination and ratio of two or more. The active ester curing agent (C) is preferably used so that the equivalent ratio of the active ester group in the curing agent to the epoxy group in the total epoxy resin in the curable resin composition is in the range of 0.2 to 2.0.

[0049] <Content of each ingredient> In the curable resin composition of the present embodiment, the content of the epoxy compound (B) is preferably 1 to 999 parts by weight, more preferably 2 to 900 parts by weight, and even more preferably 5 to 800 parts by weight, per 100 parts by weight of the epoxy compound (A). If it is equal to or more than the lower limit, the viscosity of the composition is low and a high filler loading can be achieved, whereas if it is equal to or less than the upper limit, the moisture absorption rate of the cured product of the curable resin composition is low and electrical reliability is high.

[0050] In the curable resin composition of the present embodiment, the content of the active ester-based curing agent (C) is preferably 1 to 500 parts by weight relative to 100 parts by weight of the total content of the epoxy compound (A) and the epoxy compound (B). It is more preferably 10 to 300 parts by weight, and even more preferably 50 to 200 parts by weight. When it is equal to or more than the lower limit, the dielectric properties of the cured product are excellent, and when it is equal to or less than the upper limit, the adhesiveness of the cured product is excellent.

[0051] The curable resin composition of the present embodiment contains at least the epoxy compound (A) which is one embodiment of the present invention described above, the epoxy compound (B), and the active ester-based curing agent (C). In addition, the curable resin composition of the present embodiment may be appropriately blended with other epoxy resins or curing agents described below, as well as various additives such as inorganic fillers, coupling agents, and antioxidants, as necessary.

[0052] <Other epoxy resins (D)> The curable composition of this embodiment may contain an epoxy resin (D) other than the epoxy compound (A) and the epoxy compound (B) (hereinafter referred to as other epoxy resin (D)). By using the other epoxy resin (D), it is possible to compensate for insufficient physical properties or improve various physical properties.

[0053] The other epoxy resin (D) is not particularly limited, but is preferably one having two or more epoxy groups in the molecule, and for example, various epoxy resins such as bisphenol A type epoxy resin, bisphenol AF type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol Z type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, etc. These can be used alone or as a mixture of two or more.

[0054] In the curable resin composition of this embodiment, when the composition further contains another epoxy resin (D), the amount of the other epoxy resin (D) in 100 mass% of the total epoxy resin component as a solid content is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, while it is preferably 99 mass% or less, more preferably 95 mass% or less, and even more preferably 90 mass% or less. By the ratio of the other epoxy resin (D) being the above lower limit value or more, the physical property improvement effect by blending the other epoxy resin (D) can be sufficiently obtained. On the other hand, by the ratio of the other epoxy resin (D) being the above upper limit value or less, the effects of the epoxy compound (A) and the epoxy compound (B) are fully exhibited, which is preferable from the viewpoint of obtaining the physical property improvement effect such as high heat resistance and low dielectric characteristic resistance.

[0055] <Curing agents (E) other than active ester-based curing agents (C)> From the viewpoint of improving the curability of the resin composition, the curable composition of the present embodiment preferably further contains a curing agent (E) other than the active ester-based curing agent (C) (hereinafter, may be referred to as the other curing agent (E)). In this specification, the curing agent refers to a substance that contributes to the crosslinking reaction and / or the chain extension reaction between epoxy groups of an epoxy resin. In this specification, even a substance that is usually called a "curing accelerator" is considered to be a curing agent as long as it contributes to the crosslinking reaction and / or the chain extension reaction between epoxy groups of an epoxy resin. The curing agent (E) other than the active ester-based curing agent (C) used in the curable resin composition of this embodiment is not particularly limited, and any generally known epoxy resin curing agent can be used. For example, phenol-based curing agents, amide-based curing agents, radical polymerizable resins, imidazole-based curing agents, amine-based curing agents, acid anhydride-based curing agents, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, carbodiimides, etc. can be mentioned. Among the other curing agents (E) listed above, from the viewpoint of enhancing heat resistance, phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, radical polymerizable resins, imidazole-based curing agents, cyanate ester-based curing agents, isocyanate-based curing agents, and benzoxazine-based curing agents are preferred, and phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and radical polymerizable resins are more preferred. The other curing agents (E) listed above may be used alone or as a mixture of two or more kinds in any combination and ratio.

[0056] The content of the curing agent (E) other than the active ester curing agent (C) is preferably 0.01 to 1000 parts by weight relative to 100 parts by weight of the total content of the epoxy compound (A), the epoxy compound (B) and the active ester curing agent (C) in the curable resin composition of the present invention. It is more preferably 0.1 to 800 parts by weight, and even more preferably 0.5 to 500 parts by weight. When it is equal to or more than the lower limit, the cured product has excellent hydrolysis resistance, and when it is equal to or less than the upper limit, the adhesiveness is excellent.

[0057] (Phenol-based hardener) Examples of phenol-based curing agents include various polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, trisphenol methane type resins, naphthol novolac resins, brominated bisphenol A, and brominated phenol novolac resins. Examples of such phenol resins include polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols, co-condensation resins of heavy oil or pitches with phenols and formaldehydes, phenol-benzaldehyde-xylylene dimethoxide polycondensate, phenol-benzaldehyde-xylylene dihalide polycondensate, phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensate, and phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensate. These may be used alone or in combination of two or more.

[0058] (Amine-based hardener) Specific examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and may be tertiary amines.

[0059] Examples of aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra(hydroxyethyl)ethylenediamine.

[0060] Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamines.

[0061] Examples of the alicyclic amines include isophorone diamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine.

[0062] Aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane ... Examples of such an aminophenyl amine include diphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, and 4,4'-dimethylaminopyridine.

[0063] The amine-based resins listed above may be used alone or in combination of two or more.

[0064] (Amide-based hardener) Examples of the amide-based curing agent include dicyandiamide and its derivatives, polyamide resins, etc. The amide-based curing agent may be used alone or in any combination and ratio of two or more kinds.

[0065] (Imidazole-based hardener)

[0066] Imidazole-based hardeners include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl Examples of the imidazoles include 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles. Since imidazoles have catalytic activity, they can generally be classified as curing accelerators, which will be described later, but in the present invention, they are classified as curing agents.

[0067] The imidazoles listed above may be used alone or in any combination and ratio of two or more. The imidazoles are preferably used in an amount of 0.1 to 20% by mass based on the total amount of the epoxy resin components and the imidazoles as solid contents in the curable composition.

[0068] (Acid anhydride curing agent) Specific examples of acid anhydride-based curing agents include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic) anhydride, poly(phenylhexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhimic anhydride, and trialkyltetrahydrophthalic anhydride. Anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, HET anhydride, Nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc. The amine resins listed above may be used alone or in combination of two or more kinds. The above may be used in combination.

[0069] (Cyanate ester hardener) Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. The cyanate ester curing agent may be used alone or in combination of two or more kinds.

[0070] (Isocyanate-based hardener) The isocyanate-based curing agent may be a resin having one or more isocyanate groups in the molecule. The isocyanate resin preferably has two or more isocyanate groups in the molecule. Examples of the isocyanate resin include 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate. The isocyanate-based curing agent may be used alone or in combination of two or more.

[0071] (Benzoxazine-based hardener) Examples of benzoxazine-based curing agents include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. The benzoxazine-based curing agent may include a structure in which the oxazine ring is ring-opened and polymerized. The benzoxazine-based curing agent may be used alone or in combination of two or more kinds.

[0072] (Radical polymerizable resin) As the radical polymerizable resin component, a compound that can be polymerized by radicals generated by heat or light, that is, a compound having a radical polymerizable substituent, can be used. Examples of the radical polymerizable substituent include a group having an ethylenic double bond that exhibits curability by irradiation with active energy rays. Such a radical polymerizable substituent is preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a butadiene group, more preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, and a butadiene group, further preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, and an allyl group, and particularly preferably at least one selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, and a styryl group. The radical polymerizable resin preferably has one or more radical polymerizable substituents, and more preferably has two or more radical polymerizable substituents. There is no particular upper limit, but it may be 10 or less.

[0073] [Maleimide radical polymerizable compounds] A maleimide radical polymerizable compound has at least one maleimide group in the molecule. The maleimide radical polymerizable compound preferably has one or more maleimide groups per molecule, more preferably has two or more maleimide groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0074] Examples of the maleimide radical polymerizable compound include 4,4'-diphenylmethane Examples of the bismaleimide include bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and 1,6-bismaleimide(2,2,4-trimethyl)hexane. Polyphenylmethanemaleimide is a polymer in which three or more benzene rings substituted with maleimide groups are linked via methylene groups. As the maleimide-based radical polymerizable compound, from the viewpoint of obtaining a cured product excellent in heat resistance and low dielectric properties, 4,4'-diphenylmethane bismaleimide, polyphenylene Polyphenylmethanemaleimide and 1,6-bismaleimide(2,2,4-trimethyl)hexane are more preferred.

[0075] The maleimide radical polymerizable compound may be a commercially available product. Examples of commercially available maleimide radical polymerizable compounds include "BMI-1100" (4,4'-diphenylmethane bismaleimide) and "BMI-2300" (polyphenylmethane maleimide) manufactured by Yamato Chemical Industry Co., Ltd., "BMI-TMH" (1,6-bismaleimide (2,2,4-trimethyl) hexane) represented by the following formula (5), and "BMI-TMH" (1,6-bismaleimide (2,2,4-trimethyl) hexane) represented by the following formula (6). Examples of such BMIs include "BMI-689" manufactured by Nippon Kayaku Co., Ltd., "BMI-1500" represented by the following formula (7), "BMI-1700" represented by the following formula (8), "BMI-3000" and "BMI-5000" represented by the following formula (9), "BMI-6100" represented by the following formula (10), "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., represented by the following formula (11), "MIR-5000" represented by the following formula (12), "BMI-70" manufactured by Keiai Chemical Co., Ltd., represented by the following formula (13), and "BMI-80" represented by the following formula (14).

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] In the above formula (7), a1 is an integer of 1 to 10.

[0080] [ka]

[0081] In the above formula (8), a2 is an integer of 1 to 10.

[0082] [ka]

[0083] In the above formula (9), a3 is an integer of 1 to 10.

[0084] [ka]

[0085] In the above formula (10), a4 and a5 each independently represent an integer of 10 to 35.

[0086] [ka]

[0087] In the above formula (11), a6 is an integer of 1 to 10.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [(Meth)acrylic radical polymerizable compound] (Meth)acrylic radical polymerizable compounds are compounds that contain acryloyl and methacryloyl groups. It is a compound containing a group. The (meth)acrylic radical polymerizable compound preferably has one acryloyl group and one methacryloyl group per molecule, and more preferably has two or more acryloyl groups and two or more methacryloyl groups per molecule. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0092] The (meth)acrylic radical polymerizable compound may be a commercially available product, and examples thereof include "SA9000" manufactured by SABIC, "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd., which are represented by the following formula (15).

[0093] [ka]

[0094] In the above formula (15), a7 and a8 each independently represent an integer of 0 to 300.

[0095] [Styryl radical polymerizable compounds] The styryl radical polymerizable compound is a compound having at least one styryl group represented by the following formula (16) in the molecule. The styryl radical polymerizable compound preferably has one or more styryl groups per molecule, more preferably has two or more styryl groups. There is no particular lower limit, but it is preferably 10 or less, more preferably 5 or less.

[0096] [ka]

[0097] The styryl radical polymerizable compound is not particularly limited, and examples thereof include polycondensates of the above-mentioned phenol resins and chloromethylstyrene.

[0098] As the styryl radical polymerizable compound, a commercially available product may be used, for example, "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, Inc., which is represented by the following formula (17). The styryl radical polymerizable compound may be used alone or in combination of two or more kinds.

[0099] [ka]

[0100] In the above formula (17), a9 and a10 each independently represent an integer of 0 to 300.

[0101] [Allyl radical polymerizable compounds] The allyl radical polymerizable compound is a compound having at least one allyl group in the molecule. The allyl radical polymerizable compound preferably has one or more allyl groups per molecule, more preferably has two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0102] The allyl-based radical polymerizable compound is more preferably one or more resins selected from the group consisting of a phenolic hydroxyl group-containing allyl-based radical polymerizable compound, a carboxy group-containing allyl-based radical polymerizable compound, an epoxy group-containing allyl-based radical polymerizable compound, a benzoxazine ring-containing allyl-based radical polymerizable compound, an isocyanuric ring-containing allyl-based radical polymerizable compound, and an ester group-containing allyl-based radical polymerizable compound.

[0103] The allyl radical polymerizable compound may be a commercially available product, for example, Meiwa Kasei's "MEH-8000H" and "MEH-8005", Daiwa Kasei's "DABPA" (phenolic hydroxyl group-containing allyl radical polymerizable compound), Nippon Kayaku's "RE-810NM" (epoxy group-containing allyl radical polymerizable compound), Shikoku Kasei Corporation's "ALP-d" (benzoxazine ring-containing allyl radical polymerizable compound), Shikoku Kasei Corporation's "L-DAIC", Nissan Chemical Industries, Ltd.'s "TAIC" (isocyanuric ring-containing allyl radical polymerizable compound), Osaka Soda's "MDAC", Nisshoku Techno Fine Chemical's "DAD", Osaka Soda's "Daiso DAP Monomer" (ester group-containing allyl radical polymerizable compound), and the like.

[0104] [Butadiene-based radical polymerizable compounds] The butadiene radical polymerizable compound is a compound having at least one butadiene skeleton in the molecule. The butadiene structure may be included in the main chain or in the side chain. The butadiene structure may be partially or entirely hydrogenated. As the butadiene radical polymerizable compound, one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin are more preferable.

[0105] Specific examples of butadiene-based radical polymerizable compounds include "JP-100" manufactured by Nippon Soda Co., Ltd., "Ricon100", "Ricon150", and "Ri con130MA8”, “Ricon130MA13”, “Ricon130MA20” ", "Ricon131MA5", "Ricon131MA10", "Ricon131M A17", "Ricon131MA20", "Ricon184MA6", etc. can be.

[0106] <Solvent> In order to ensure the handling and workability in molding the curable resin composition, the curable resin composition of this embodiment may be diluted with a solvent in order to appropriately adjust the viscosity of the curable resin composition, and the amount of the solvent used is not particularly limited. In the present invention, the term "solvent" and the above-mentioned term "solvent" are used separately depending on the form of use, but the same or different solvents may be used independently.

[0107] Examples of the solvent that may be contained in the curable resin composition of the present embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone, and ethyl acetate. Examples of the solvent include esters such as ethylene glycol monomethyl ether, ethers such as ethylene glycol monomethyl ether, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene. The above-mentioned solvents may be used alone or in any combination and ratio of two or more.

[0108] <Other ingredients> The curable resin composition of the present embodiment may contain components other than those listed above (hereinafter, sometimes referred to as "other components") for the purpose of further improving its functionality. Examples of other components include thermosetting resins and photocurable resins other than epoxy resins, curing accelerators (excluding those included in "curing agents"), ultraviolet inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, inorganic fillers, and organic fillers.

[0109] The resin composition of the present invention can be prepared by appropriately mixing the above components, and kneading or mixing them as necessary with a kneading means such as a triple roll mill, a ball mill, a bead mill, a sand mill, or a stirring means such as a super mixer, a planetary mixer, etc. Furthermore, it can also be prepared as a resin varnish by further adding an organic solvent.

[0110] [Cured product] One embodiment of the present invention is a cured product obtained by curing the curable resin composition according to one embodiment of the present invention. The cured product according to this embodiment is advantageous for fine wiring, multi-layering, high density, high frequency, etc. of electronic components because of its excellent heat resistance and low dielectric properties. In addition, by obtaining a curable resin composition with excellent handling properties, it is possible to increase the amount of filler added and improve the impregnation of glass cloth. The term "curing" as used herein means intentionally curing the curable composition by heat and / or light, etc., and the degree of curing may be controlled according to the desired physical properties and applications. The degree of progress of the curing reaction may be completely cured or semi-cured, and is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.

[0111] The curing method of the curable resin composition when producing the cured product of this embodiment varies depending on the components and amounts in the curable resin composition, but typically includes heating conditions of 80 to 280°C for 60 to 360 minutes. This heating is preferably performed in two stages, with a primary heating at 80 to 160°C for 10 to 90 minutes and a secondary heating at 120 to 200°C for 60 to 150 minutes, and in a compounding system in which the glass transition temperature (Tg) exceeds the secondary heating temperature, it is preferable to further perform a tertiary heating at 150 to 280°C for 60 to 120 minutes. Performing the secondary and tertiary heating in this manner is preferable from the viewpoint of reducing poor curing and residual solvent.

[0112] When preparing a semi-cured resin product, it is preferable to proceed with the curing reaction of the curable composition to such an extent that the shape can be maintained by heating, etc. When the curable composition contains a solvent, most of the solvent is usually removed by a method such as heating, reducing pressure, or air drying, but 5% by mass or less of the solvent may remain in the semi-cured resin product.

[0113] [Application] A cured product using the curable resin composition of the present embodiment has low moisture absorption and excellent electrical reliability when used as an electronic material, has a high glass transition temperature and excellent heat resistance, and has a low elastic modulus at high temperatures and excellent performance in relaxing stress caused by temperature changes.

[0114] Therefore, the curable resin composition of the present embodiment and the cured product thereof can be effectively used in any application that requires these physical properties. For example, optical materials, automobiles, etc. They can be suitably used in a wide range of applications, including automotive paints such as electrocoating paints for automobiles, heavy-duty anticorrosive paints for ships and bridges, and paints for coating the inside of beverage cans; electrical and electronic applications such as composite materials, laminates, semiconductor sealants, liquid insulating sealants, and other sealants, insulating powder paints, and coil impregnation; and civil engineering, construction, and adhesive applications such as earthquake-resistant reinforcement of bridges, concrete reinforcement, building flooring, water facility linings, drainage and permeable pavements, and adhesives for structures, vehicles, and aircraft. Among these, they are particularly useful for electrical and electronic parts.

[0115] The curable resin composition of the present invention may be used for the above-mentioned applications after curing, or may be cured during the production process for the above-mentioned applications.

[0116] [Laminate] A method for producing a laminate using the curable resin composition of the present embodiment includes a method for producing a laminate by heating and pressurizing a laminate including a prepreg in which a fibrous substrate is impregnated with the resin varnish comprising the curable resin composition of the present invention to produce a laminate.

[0117] More specifically, a fibrous substrate is impregnated with a resin varnish, dried, and the solvent is removed to obtain a prepreg. This prepreg is laminated with other substrates as required to form a laminate, which is then cured by heating and pressurizing to obtain a laminate.

[0118] The number of layers of the prepreg in the laminate may be one or more. In the laminate, a base material other than the prepreg may be laminated. Examples of the base material include a metal foil such as a copper foil.

[0119] Examples of fibers constituting the fibrous substrate include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and stainless steel fibers; natural fibers such as cotton, hemp, and paper; and synthetic organic fibers such as polyester resins and polyamide resins. Any one of these fibers may be used alone, or two or more of them may be used in combination.

[0120] The shape of the fibrous base material is not particularly limited, and examples thereof include staple fibers, yarns, mats, sheets, and the like.

[0121] The amount of resin varnish to be impregnated into the fibrous base material is not particularly limited, and for example, the solid content of the resin varnish to be impregnated is set to about 30 to 50 mass % with respect to the fibrous base material (100 mass %). The heating temperature when the laminate is heated and pressed is preferably the above-mentioned curing temperature. 2 is preferred.

[0122] The laminate thus manufactured includes a fiber-reinforced resin layer including a fibrous base material and a cured product of a resin varnish. The number of fiber-reinforced resin layers included in the laminate may be one layer or two or more layers. As described above, the laminate may include a metal foil layer such as a copper foil.

[0123] [Sealing material] When the curable resin composition of the present embodiment is used as an encapsulant, the shape of the encapsulant is not particularly limited, and for example, the same shape as that used in known semiconductors or the like can be used. Examples of a method for forming an encapsulant using the curable resin composition of the present invention include methods for encapsulating a semiconductor using transfer molding, compression molding, or the like. EXAMPLES

[0124] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In addition, various production conditions and evaluation results in the following examples The values ​​have the meaning of preferred upper or lower limit values ​​in the embodiment of the present invention, and a preferred range may be a range defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following examples or values ​​of the examples.

[0125] [Physical properties and characteristics evaluation method] [Measurement and evaluation method] The physical properties of the curable resin compositions and their cured products obtained in the following Examples and Comparative Examples were measured and evaluated as follows.

[0126] <Dielectric properties> The cured product (film) was cut into test pieces with a width of 2 mm and a length of 80 mm, and the dielectric properties (relative dielectric constant: Dk) of the test pieces were measured at measurement frequencies (1 GHz and 10 GHz) by the cavity resonance perturbation method using a network analyzer. Details of the equipment used and the measurement environment are shown below. Note that the dielectric properties were calculated using dedicated measurement software provided by the manufacturer of the cavity resonator. Equipment used: Network analyzer: Agilent Technologies E8361A Cavity resonator CP215 (1GHz), CP184 (10GHz) manufactured by Kanto Electronics Application Development Co., Ltd. Measurement environment: Temperature 23℃, relative humidity 50%RH

[0127] <Glass transition temperature (Tg)> The cured product (film) was cut into a test piece measuring 2.5 cm in length and 4 mm in width, and using the obtained test piece, a thermomechanical analysis (TMA: Thermomechanical Analyzer) was carried out under the following conditions to calculate the glass transition temperature (Tg). Analytical equipment: HITACHI TMA7100 Measurement mode: Tensile mode Measurement temperature range: 30℃ to 250℃ Temperature program: 30℃ → 180℃ 10℃ / min 180℃ → -10℃ 10℃ / min -10℃ → 250℃ 5℃ / min

[0128] <Storage modulus E'(40℃)> The cured product (film) was cut into a test piece measuring 5 cm in length and 1 cm in width, and dynamic mechanical analysis (DMA) was performed under the following conditions to measure the storage modulus (E') at 40°C. Analytical equipment: HITACHI DMA7100 Measurement mode: Tensile mode Measurement temperature range: 30℃ to 250℃ Heating rate: 5℃ / min

[0129] [Raw materials, etc.] The raw materials and their synthesis methods used in the following Examples and Comparative Examples are as follows.

[0130] [Production Example 1] 220g of xylene and 130g of sulfuric acid were charged into a 2L three-neck flask equipped with a thermometer, a stirrer, and a cooling tube, and the mixture was heated to 90°C to dissolve uniformly. Then, 240g of 35% aqueous formaldehyde solution was added dropwise over 1 hour. After the addition was complete, the mixture was kept at 90°C for 5 hours to complete the reaction, and the sulfuric acid was removed by washing with water. After repeated washing with water until the system became neutral, the product was The xylene was then distilled off under reduced pressure to obtain a xylene-formaldehyde resin. The olefin-formaldehyde resin is referred to as XF resin.

[0131] In a 2L three-neck flask equipped with a thermometer, stirrer, and condenser, 200g of the XF resin obtained above was added with 300g of phenol and 0.1g of p-toluenesulfonic acid, and the mixture was stirred at 100°C for 2 hours. Then, 35g of formalin and 1.5g of oxalic acid were added and the mixture was stirred for 3 hours. The reaction mixture was dissolved in 500g of methyl isobutyl ketone, and repeatedly washed with water at 65°C until it became neutral. Then, methyl isobutyl ketone and phenol were distilled off under reduced pressure at 160°C and under reduced pressure to obtain an aromatic hydrocarbon formaldehyde resin-modified novolac-type phenolic resin. This resin had a hydroxyl equivalent of 163g / eq., a melt viscosity of 0.21 Pa·s at 150°C, a softening point of 84°C, and a free phenol content of 0.1% by mass or less. In addition, this resin had m=2.3 and n=1.6 in the general formula (3).

[0132] 150g of the aromatic hydrocarbon formaldehyde resin-modified novolac-type phenolic resin thus obtained, 510g of epichlorohydrin, and 200g of isopropyl alcohol were charged into a 2L three-neck flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was raised to 40°C to dissolve uniformly, and then 90g of a 48.5% by mass aqueous sodium hydroxide solution was dropped over 60 minutes. During this time, the temperature was gradually raised, and the temperature inside the system was adjusted to 65°C after the end of the dropwise addition. After that, the reaction was completed by holding at 65°C for 30 minutes, and the by-product salt and excess sodium hydroxide were removed by washing with water. Next, excess epichlorohydrin and isopropanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 30g of methyl isobutyl ketone, and 9g of a 48.5% by mass aqueous sodium hydroxide solution was added and reacted at a temperature of 65°C for 1 hour. After that, an aqueous solution of sodium dihydrogen phosphate was added to the reaction solution to neutralize the excess sodium hydroxide, and the by-product salt was removed by washing with water. Next, methyl isobutyl ketone was completely removed under reduced pressure to obtain 180 g of epoxy compound (A-1). The obtained epoxy compound (A-1) had an epoxy equivalent of 283 g / eq., hydrolyzable halogen of 400 ppm, a melt viscosity at 150°C of 0.18 Pa s, and a softening point of 63°C.

[0133] [Production Example 2] In a 5L four-neck flask equipped with a thermometer, a stirrer, and a cooling tube, 200g of raw material phenol (4): tetramethylbiphenol (manufactured by Mitsubishi Chemical Corporation), 1071g of epichlorohydrin, 417g of isopropyl alcohol, and 150g of water were charged, and the temperature was raised to 40°C to dissolve uniformly, and 159g of 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 90 minutes. At the same time as the dropwise addition, the temperature was raised from 40°C to 65°C over 90 minutes. After that, the reaction was completed by holding at 65°C for 30 minutes, and the reaction liquid was transferred to a 5L separatory funnel, 300g of 65°C hot water was added, cooled to 65°C, and left to stand for 1 hour. After standing, the aqueous layer was extracted from the separated oil layer and aqueous layer, and by-product salt and excess sodium hydroxide were removed. Then, epichlorohydrin was completely removed under reduced pressure at 150°C.

[0134] Then, 439g of methyl isobutyl ketone was added and heated to 65℃ to dissolve uniformly. Then, 6.2g of 48.5% by weight aqueous sodium hydroxide solution was added and reacted for 60 minutes, after which the mixture was washed four times with 400g of water. Then, the methyl isobutyl ketone was completely removed under reduced pressure at 150℃ to obtain epoxy compound (B-1). The obtained epoxy compound (B-1) had an epoxy equivalent of 185g / eq., hydrolyzable halogen of 400ppm, a melt viscosity at 150℃ of 0.01Pa·s, and a melting point of 108℃.

[0135] [Production Example 3] An epoxy compound (B-1) was obtained by the same procedure as in Production Example 2. Then, 1000 g of the obtained epoxy compound (B-1), 1200 g of methyl isobutyl ketone, and dimethyl sulfoxide were added to a 5 L separable flask equipped with a thermometer, a stirrer, and a cooling tube. 300g of epoxy compound (B-2) was added, the reaction temperature was raised to 65℃, and the mixture was dissolved uniformly. Then, 49g of 8% by weight potassium hydroxide / isopropanol solution was added and the reaction was carried out for 2 hours. Then, 300g of methyl isobutyl ketone was added, and the mixture was washed four times with 1000g of water. Then, the methyl isobutyl ketone was completely removed under reduced pressure at 150℃ to obtain epoxy compound (B-2). The obtained epoxy compound (B-2) had an epoxy equivalent of 208g / eq., hydrolyzable halogen of 50ppm, a melt viscosity at 150℃ of 0.02Pa·s, and a melting point of 100℃.

[0136] <Production of Curable Resin Composition and Preparation of Cured Product>

[0137] In producing the curable resin composition, the following active ester-based curing agent (C), other epoxy resin (D), and curing agent (E) were further used.

[0138] [Active ester curing agent (C)] (C-1): Commercially available polyarylate resin (polyarylate having a bisphenol skeleton, active equivalent: 220 g / equivalent)

[0139] [Other epoxy resins (D)] (D-1): Polymer epoxy resin as another epoxy resin to be used as a film forming agent (manufactured by Mitsubishi Chemical, product name "YX7891T30", Mn: 10,000, Mw: 30,000, epoxy equivalent: 6,000 g / equivalent, resin content: 30% by mass)

[0140] [Hardening agent (E)] (E-1): DMAP: 4,4'-dimethylaminopyridine

[0141] [Examples 1 to 4, Comparative Examples] A commercially available polyarylate resin (C-1) was dissolved in toluene to a resin content of 40% by mass. In addition, 4,4'-dimethylaminopyridine (E-1) was dissolved in toluene to a resin content of 5% by mass. The toluene solutions of each resin and the resin prepared above were mixed as shown in Table 1 to obtain a curable resin composition. The obtained solution of the curable composition was applied to a release PET film (polyethylene terephthalate film treated with silicone) using an applicator with a thickness of 300 μm and a width of 5 cm, dried at 160°C for 1.5 hours, and then cured at 200°C for 1.5 hours to obtain a film of a cured epoxy resin. The glass transition temperature (°C), relative dielectric constant (1 GHz, 10 GHz), and storage modulus (GPa) of these were evaluated according to the above-mentioned methods. The results are also shown in Table 1.

[0142] [Table 1]

[0143] It is clear from Table 1 that Examples 1 to 4 have lower elastic moduli, higher glass transition temperatures, and lower relative dielectric constants at each measurement frequency (1 GHz and 10 GHz) than the Comparative Example.

Claims

1. A curable resin composition comprising an epoxy compound (A) represented by the following formula (1), an epoxy compound (B) represented by the following formula (2), and an active ester-based curing agent (C). 【Chemistry 1】 (In the above formula (1), m is the average number of repetitions and is 0 or more, and n is the average number of repetitions and is greater than 0.) 【Chemistry 2】

2. The curable resin composition according to claim 1, wherein the content of the epoxy compound (B) is 1 to 999 parts by weight based on 100 parts by weight of the epoxy compound (A).

3. The curable resin composition according to claim 1, wherein the content of hydrolyzable halogen in the epoxy compound (A) is 1000 ppm by weight or less.

4. The curable resin composition according to claim 1, wherein the content of the active ester-based curing agent (C) is 1 to 500 parts by weight based on 100 parts by weight of the total content of the epoxy compound (A) and the epoxy compound (B).

5. The curable resin composition according to claim 1, further comprising a curing agent (E) other than the active ester-based curing agent (C), wherein the content of the curing agent (E) is 0.01 to 1000 parts by weight relative to 100 parts by weight of the total content of the epoxy compound (A), the epoxy compound (B) and the active ester-based curing agent (C) in the curable resin composition.

6. The curable resin composition according to claim 5, wherein the curing agent (E) comprises at least one selected from the group consisting of a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, an amide-based curing agent, and a radical polymerizable resin.

7. The curable resin composition according to claim 6, wherein the radical polymerizable resin contains at least one substituent selected from the group consisting of a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a butadiene group.

8. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7.

9. An electric / electronic part obtained by curing the curable resin composition according to any one of claims 1 to 7. Product.

10. A laminate obtained by curing the curable resin composition according to any one of claims 1 to 7.

11. An encapsulant comprising the curable resin composition according to any one of claims 1 to 7.

Images