Polycrystal of bisphenol-type diglycidyl ether, resin composition comprising same, and cured product thereof

Abstract

The present invention relates to a polycrystal of a bisphenol-type diglycidyl ether, the polycrystal comprising an epoxy compound represented by formula (1), the crystallite size calculated from a peak having a diffraction angle (2 [theta]) at 8.9-9.3 deg in a powder X-ray diffraction pattern measured with a CuK [alpha] ray being # imgabs 0 # formula (1), and the crystallite size calculated from a peak having a diffraction angle (2 [theta]) at 8.9-9.3 deg. Each of R1-R8 independently represents a hydrogen atom, an optionally substituted alkyl group having 1-12 carbon atoms, an optionally substituted alkoxy group having 1-12 carbon atoms, an optionally substituted aryl group having 6-12 carbon atoms, an optionally substituted alkenyl group having 2-12 carbon atoms, or an optionally substituted alkynyl group having 2-12 carbon atoms. # imgabs1 #

Description

Technical Field

[0001] The present invention relates to a polycrystal of bisphenol-type diglycidyl ether having high handleability and being industrially advantageous, a cured product obtained by curing the polycrystal, and an electric / electronic component. Background Art

[0002] Epoxy resins, when cured with various curing agents, generally exhibit excellent mechanical, heat resistance, and electrical properties. Consequently, they are used in a wide range of fields, including adhesives, coatings, and electrical and electronic materials. In particular, tetramethylbisphenol-based epoxy resins are widely used as semiconductor encapsulation materials within the electrical and electronic fields, as they offer high-value-added encapsulation materials.

[0003] As a recent trend in semiconductor packaging material manufacturing technology, the following (1) and (2) are required.

[0004] (1) High productivity achieved by pre-dry mixing during semiconductor packaging material manufacturing

[0005] Solid packaging materials are widely used as semiconductor packaging materials from the perspective of formability and storage properties. However, in order to improve the production efficiency during the manufacture of semiconductor packaging materials and to increase the uniformity of the packaging materials, a method of homogenizing the raw material components by pre-dry mixing has been adopted. The epoxy resins, curing agents, and inorganic fillers used as raw materials also prefer to be solid and powdery raw materials.

[0006] (2) Low melt viscosity due to crystalline raw materials

[0007] As semiconductors become increasingly miniaturized, the wires connecting IC chips are becoming thinner. To prevent wire displacement in semiconductor packaging materials that protect the wires, high fluidity is required. Consequently, crystalline epoxy resins with lower melt viscosities are preferred among solid epoxy resins used as raw materials.

[0008] Patent Documents 1 and 2 describe the production of a tetramethylbisphenol-type epoxy resin by reacting 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl with epichlorohydrin.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 58-039677

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 2004-315832 Summary of the Invention

[0013] Semiconductor packaging materials are manufactured by pre-mixing epoxy resin, curing agent and inorganic filler as raw materials using dry mixing, and then utilizing kneader and hot roller to carry out melt mixing. In the past, non-crystalline epoxy resin was used as epoxy resin, but there was the following problem: the softening point of non-crystalline epoxy resin was relatively low, and when pre-mixing was carried out using dry mixing, solid raw materials would adhere to each other and produce lumps, which was difficult for homogenization, and because the melt viscosity was high, the productivity of melt mixing was low. Therefore, in order to solve the above two problems simultaneously, the industrialization of powdered crystalline epoxy resin is desired. The melting point of crystalline epoxy resin is high enough, and lumps will not be produced during dry mixing, and the melt viscosity is low, so raw materials are uniformly mixed with each other in a short time during mixing, and the improvement of productivity can be expected.

[0014] Furthermore, to increase processing speed, semiconductor components are becoming increasingly miniaturized. This is driven by the continued thinning of wires connecting IC chips. To prevent wire misalignment, semiconductor packaging materials that protect IC chips are required to have low viscosity. Crystalline epoxy resins, with their low viscosity, are expected to be suitable raw materials for this purpose.

[0015] The epoxy resin described in Patent Document 1 does not fully satisfy the handleability during dry mixing of solid raw materials, which is key to productivity, in a process for efficiently producing a powdered epoxy resin as a crystalline raw material for semiconductor encapsulation materials on an industrial scale and using the epoxy resin to produce a cured product.

[0016] In the industrial-scale production of epoxy resin crystals, the crystallization process is generally susceptible to the influence of the surface material and shape of the packaging material and the air interface. The method for producing crystals described in Patent Document 2 is particularly susceptible to these influences. Therefore, the influence of the long crystallization process, which is crucial for homogeneous crystallization throughout the interior of the crystals and is required for pulverization of the crystals, on the crystals remains unclear, and it remains unclear whether crystals with homogeneous crystallization properties that can withstand industrial-scale pulverization can be obtained.

[0017] Therefore, an object of the present invention is to provide a polycrystal of bisphenol diglycidyl ether, which has excellent crushability and fluidity and can improve productivity in the production of epoxy resins, semiconductor packaging materials, etc., a resin composition containing the polycrystal, a cured product composed of the resin composition, and an electric / electronic component.

[0018] The present inventors have conducted intensive studies to solve the above problems and have found that polycrystalline bisphenol diglycidyl ether can solve the above problems by adjusting the crystallite size calculated from the peaks detected by powder X-ray diffraction to a specific value, thereby completing the present invention.

[0019] That is, the gist of the present invention lies in the following [1] to

[10] .

[0020] [1] A polycrystalline bisphenol diglycidyl ether comprising an epoxy compound represented by the following formula (1), wherein the crystallite size calculated from a peak having a diffraction angle (2θ) of 8.9 to 9.3 degrees in a powder X-ray diffraction pattern measured using CuKα radiation is

[0021]

[0022] (In the above formula (1), R 1 ~R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, or an alkynyl group having 2 to 12 carbon atoms which may have a substituent.

[0023] [2] The polycrystal of bisphenol diglycidyl ether according to [1], wherein the average particle size is 0.5 to 10,000 μm.

[0024] [3] The polycrystal of bisphenol diglycidyl ether according to [1] or [2], which is a crushed product.

[0025] [4] The polycrystalline form of bisphenol diglycidyl ether according to any one of [1] to [3], wherein the melting point is 80° C. or higher.

[0026] [5] The polycrystal of bisphenol diglycidyl ether according to any one of [1] to [4], wherein the crystallite size calculated from the peak having a diffraction angle (2θ) of 15.1 to 15.5 degrees in the powder X-ray diffraction pattern measured by CuKα radiation is

[0027] [6] The polycrystal of bisphenol diglycidyl ether according to any one of [1] to [5], further comprising diffraction peaks at diffraction angles (2θ) of 15.1 to 15.5 degrees, 19.4 to 19.8 degrees, and 24.9 to 25.3 degrees in a powder X-ray diffraction pattern measured using CuKα radiation.

[0028] [7] The polycrystalline form of bisphenol diglycidyl ether according to any one of [1] to [6], further comprising an epoxy compound represented by the following formula (2).

[0029]

[0030] (In the above formula (2), R 11 ~R 18 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, or an alkynyl group having 2 to 12 carbon atoms which may have a substituent; R 19 ~R 21 Each of the above R is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent, 19 With the above R 20 They can bond to each other to form a ring structure with 1 to 12 carbon atoms.

[0031] [8] A resin composition comprising a polycrystal of bisphenol diglycidyl ether according to any one of [1] to [7] and a curing agent, wherein the curing agent is contained in an amount of 0.01 to 1000 parts by mass per 100 parts by mass of the total epoxy resin component as a solid content.

[0032] [9] The resin composition according to [8], wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent.

[0033]

[10] A cured product of the resin composition described in [8] or [9].

[0034]

[11] An electric or electronic component comprising a resin composition containing a polycrystal of the bisphenol diglycidyl ether according to any one of [1] to [7].

[0035]

[12] An electric or electronic component comprising a cured product of a resin composition containing a polycrystal of the bisphenol-type diglycidyl ether according to any one of [1] to [7].

[0036] According to the present invention, a polycrystalline bisphenol diglycidyl ether having excellent pulverizability and fluidity can be obtained. This polycrystalline bisphenol diglycidyl ether has excellent pulverizability on an industrial scale, a melting point within an ideal range from the perspective of semiconductor production, and excellent fluidity. Therefore, it is expected that industrial handling properties will be improved, particularly in semiconductor production. DETAILED DESCRIPTION

[0037] Hereinafter, an embodiment of the present invention will be described in detail. The following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the invention.

[0038] In this specification, when an expression such as "to" is used, it is used as an expression including the numerical values or physical property values before and after it.

[0039] The epoxy resins of this embodiment include those having a repeating structure and those having a single molecular structure. In the epoxy resin industry, either epoxy compound is sometimes referred to and sold as an "epoxy resin" or an "epoxy resin composition." Furthermore, in the epoxy resin industry, mixtures further comprising an epoxy resin different from the epoxy resin of this embodiment are sometimes referred to as "epoxy resin compositions" or simply as "epoxy resins."

[0040] [Polycrystalline bisphenol diglycidyl ether]

[0041] The polycrystal of bisphenol-type diglycidyl ether according to one embodiment of the present invention (hereinafter sometimes referred to as "polycrystal of bisphenol-type diglycidyl ether") is characterized by comprising an epoxy compound represented by the following formula (1) (hereinafter sometimes referred to as "epoxy compound (1)" or "epoxy resin (1)"), and having a crystallite size calculated from a peak having a diffraction angle (2θ) of 8.9 to 9.3 degrees in a powder X-ray diffraction pattern measured with CuKα radiation of 0.1 to 0.2 degrees.

[0042]

[0043] R 1 ~R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. The alkyl group, alkoxy group, aryl group, alkenyl group, and alkynyl group may or may not have a substituent.

[0044] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, and 2-phenylisopropyl.

[0045] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a neopentoxy group, a tert-pentoxy group, a cyclopentyloxy group, an n-hexyloxy group, an isohexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, a cycloheptyloxy group, a methylcyclohexyloxy group, an n-octyloxy group, a cyclooctyloxy group, an n-nonyloxy group, a 3,3,5-trimethylcyclohexyloxy group, an n-decyloxy group, a cyclodecyloxy group, an n-undecyloxy group, an n-dodecyloxy group, a cyclododecyloxy group, a benzyloxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a naphthylmethoxy group, a phenethoxy group, and a 2-phenylisopropoxy group.

[0046] Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, cyclohexenyl, cyclohexadienyl, cinnamyl, and naphthylvene.

[0047] Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butadiynyl, phenylethynyl, and naphthylethynyl.

[0048] Examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethynylphenyl, naphthyl, and vinylnaphthyl.

[0049] R 1 ~R 8 Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent, more preferably each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent, further preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0050] In R 1 ~R 8 In the present invention, the substituents that the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkenyl group having 2 to 12 carbon atoms or the alkynyl group having 2 to 12 carbon atoms may have are not particularly limited. For example, a cyano group, an amino group, a carboxyl group, an ester group, an alkylcarbonyl group, an acetyl group, a sulfonyl group, a silyl group, a borane group, a thio group or a seleno group may be mentioned. From the viewpoint of reducing the water absorption of the cured product, an ester group, an alkylcarbonyl group or a silyl group is preferred.

[0051] The polycrystalline body of bisphenol diglycidyl ether may be a pulverized body. In this specification, a pulverized body refers to a body obtained by pulverization, and specifically, preferably a granular body having an average particle size of 5 cm or less. The following describes the conditions for the parameters of the polycrystalline body's size; these conditions are particularly preferred when the polycrystalline body is a pulverized body.

[0052] The average particle size of the polycrystals of bisphenol diglycidyl ether is not particularly limited, but is generally 0.5 μm or greater, preferably 1 μm or greater. The lower limit of this average particle size is more preferably 5 μm or greater, and even more preferably 20 μm or greater. When the average particle size is within the above lower limit, adhesion of fine powder to equipment such as the pulverizing apparatus and the generation of dust during pulverization and other processes can be easily prevented.

[0053] The average particle size of the polycrystals of bisphenol diglycidyl ether is preferably 10,000 μm or less. The upper limit of this average particle size is more preferably 5,000 μm or less, and even more preferably 2,000 μm or less. When the average particle size is below the upper limit of the aforementioned range, the polycrystals are easily melted quickly during melt kneading during the manufacture of semiconductor packaging materials and are easily homogenized when mixed with other epoxy resins, curing agents, inorganic fillers, and the like.

[0054] The D10 value of the polycrystalline bisphenol diglycidyl ether is not particularly limited, but is preferably 0.1 μm or greater. The lower limit of the D10 value is more preferably 1 μm or greater, and even more preferably 10 μm or greater. When the D10 value is within the above lower limit, adhesion of fine powder to equipment such as the pulverizing apparatus and the generation of dust during pulverization and other processes can be easily prevented.

[0055] The D10 value of the polycrystalline bisphenol diglycidyl ether is preferably 1000 μm or less. The upper limit of the D10 value is more preferably 800 μm or less, and even more preferably 500 μm or less. When the D10 value is below the upper limit of the above range, the polycrystalline bisphenol diglycidyl ether is easily melted in a short time during melt kneading during the manufacture of semiconductor packaging materials, and is easily homogenized when mixed with other epoxy resins, curing agents, inorganic fillers, etc.

[0056] The D50 value of the polycrystalline bisphenol diglycidyl ether is not particularly limited, but is preferably 1 μm or greater. The lower limit of the D50 value is more preferably 5 μm or greater, and even more preferably 20 μm or greater. When the D50 value is within the above lower limit, adhesion of fine powder to equipment such as the pulverizing apparatus and the generation of dust during pulverization and other processes can be easily prevented.

[0057] The D50 value of the polycrystalline bisphenol diglycidyl ether is preferably 10,000 μm or less. The upper limit of the D50 value is more preferably 5,000 μm or less, and even more preferably 2,000 μm or less. When the D50 value is below the upper limit of the above range, the polycrystalline bisphenol diglycidyl ether is easily melted in a short time during melt kneading during the manufacture of semiconductor packaging materials, and is easily homogenized when mixed with other epoxy resins, curing agents, inorganic fillers, etc.

[0058] The D90 value of the polycrystalline bisphenol diglycidyl ether is not particularly limited, but is preferably 5 μm or greater. The lower limit of the D90 value is more preferably 10 μm or greater, and even more preferably 30 μm or greater. When the D90 value is within the above lower limit, adhesion of fine powder to equipment such as the pulverizing apparatus and the generation of dust during pulverization and other processes can be easily prevented.

[0059] The D90 value of the polycrystalline bisphenol diglycidyl ether is preferably 20,000 μm or less. The upper limit of the D90 value is more preferably 10,000 μm or less, and even more preferably 3,000 μm or less. When the D90 value is below the upper limit of the above range, the polycrystalline bisphenol diglycidyl ether is easily melted in a short time during melt kneading during the manufacture of semiconductor packaging materials, and is easily homogenized when mixed with other epoxy resins, curing agents, inorganic fillers, etc.

[0060] The average particle size, D10 value, D50 value, and D90 value of the pulverized product of the polycrystal can be measured, for example, by a laser scattering method or a sieving method.

[0061] The melting point of the polycrystals of bisphenol diglycidyl ether is not particularly limited, but is preferably 80°C or higher. The lower limit of the melting point is more preferably 85°C or higher, and even more preferably 90°C or higher. When the melting point is within the range above the lower limit, melting due to heat generated during the pulverization of the polycrystals and sticking within the apparatus are less likely to occur.

[0062] The melting point of the polycrystalline bisphenol diglycidyl ether is preferably 150°C or lower. The upper limit of the melting point is more preferably 140°C or lower, and even more preferably 130°C or lower. When the melting point is below the upper limit of the above range, the polycrystalline bisphenol diglycidyl ether is easily melted in a short time during melt kneading during the production of semiconductor packaging materials, and is easily homogenized when mixed with other epoxy resins, curing agents, inorganic fillers, etc.

[0063] In addition, when the polycrystalline form of bisphenol diglycidyl ether has two or more melting points, it is preferred that any one of the plurality of melting points satisfy the above range, and it is more preferred that all of the melting points satisfy the above range.

[0064] The content of the epoxy resin (1) in the polycrystal of bisphenol diglycidyl ether is not particularly limited, but is preferably 70.0 to 99.9 mass%, more preferably 75.0 to 98.0 mass%, and even more preferably 80.0 to 95.0 mass%, relative to 100 mass% of the polycrystal of bisphenol diglycidyl ether. If the content is at least the lower limit of the above range, polycrystals having a large crystallite size suitable for processing such as pulverization can be easily obtained. If the content is at most the upper limit of the above range, the melting point is low, and mixing of the raw materials of the semiconductor encapsulation material can be performed in a short time.

[0065] The content of the epoxy resin (1) can be evaluated by the method described in the examples below.

[0066] The polycrystal of bisphenol diglycidyl ether preferably has a diffraction peak at a diffraction angle (2θ) of 8.9 to 9.3 degrees in a powder X-ray diffraction pattern measured using CuKα radiation, and further has a diffraction peak at at least one diffraction angle (2θ) range selected from 15.1 to 15.5 degrees, 19.4 to 19.8 degrees, and 24.9 to 25.3 degrees, and more preferably has a diffraction peak at a diffraction angle (2θ) in all of these ranges.

[0067] The crystallite size of the polycrystal was calculated from the peak with a diffraction angle (2θ) of 8.9 to 9.3 degrees in the powder X-ray diffraction pattern measured with CuKα radiation. The crystallite size is preferably More preferably If the crystallite size is above the lower limit, the polycrystals are less likely to clumping during processing such as pulverization. If it is below the upper limit of the above range, the crystallite size is small, the particle size after the processing is small, and the polycrystals melt quickly when heated, that is, excellent fluidity is achieved. It should be noted that the diffraction angle of 8.9 to 9.3 degrees is less susceptible to the influence of other peaks than 15.1 to 15.5 degrees, 19.4 to 19.8 degrees, and 24.9 to 25.3 degrees, and is therefore a suitable range for calculating the crystallite size.

[0068] The crystallite size of the polycrystal calculated from the peak having a diffraction angle (2θ) of 15.1 to 15.5 degrees in the powder X-ray diffraction pattern measured with CuKα radiation is preferably More preferably More preferably If the crystallite size is above the above lower limit, adhesion of the polycrystals during treatments such as crushing will not easily occur. If it is below the upper limit of the above range, the crystallite size is smaller, the particle size after treatment becomes smaller, and the polycrystals melt in a short time when heated.

[0069] The crystallite size of the polycrystal calculated from the peak having a diffraction angle (2θ) of 19.4 to 19.8 degrees in the powder X-ray diffraction pattern measured with CuKα radiation is preferably More preferably More preferably If the crystallite size is above the above lower limit, adhesion of the polycrystals during treatments such as crushing will not easily occur. If it is below the upper limit of the above range, the crystallite size is smaller, the particle size after treatment becomes smaller, and the polycrystals melt in a short time when heated.

[0070] The crystallite size of the polycrystal calculated from the peak having a diffraction angle (2θ) of 24.9 to 25.3 degrees in the powder X-ray diffraction pattern measured with CuKα radiation is preferably More preferably More preferably If the crystallite size is above the above lower limit, adhesion of the polycrystals during treatments such as crushing will not easily occur. If it is below the upper limit of the above range, the crystallite size is smaller, the particle size after treatment becomes smaller, and the polycrystals melt in a short time when heated.

[0071] The crystallite size of the above-mentioned polycrystal can be evaluated by the method described in Examples below.

[0072] From the viewpoint of lowering the melting point and shortening the melting time, the polycrystal of bisphenol diglycidyl ether preferably contains an epoxy compound represented by the following formula (2) (hereinafter sometimes referred to as "epoxy compound (2)" or "epoxy resin (2)").

[0073]

[0074] In the above formula (2), R 11 ~R 18 Respectively with R in the above formula (1) 1 ~R 8 Same meaning.

[0075] R 19 ~R 21 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the alkyl group and the aryl group may have a substituent. 19 With R 20 They may bond to each other to form a ring structure having 1 to 12 carbon atoms.

[0076] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, and 2-phenylisopropyl.

[0077] Examples of the aryl group having 6 to 12 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethynylphenyl, naphthyl, and vinylnaphthyl.

[0078] R 19 With R 20 When the cyclic structures are bonded to each other, they preferably form a cyclic ketone structure having 3 to 12 carbon atoms. Examples of such cyclic structures include cyclopropanone, cyclobutanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, and cyclododecanone.

[0079] R 19 ~R 21 Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent, more preferably each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and most preferably R9 is an isobutyl group. 20 and R 21 A hydrogen atom.

[0080] In R 19 ~R 21 In the present invention, the substituents that the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkenyl group having 2 to 12 carbon atoms or the alkynyl group having 2 to 12 carbon atoms may have are not particularly limited. For example, a cyano group, an amino group, a carboxyl group, an ester group, an alkylcarbonyl group, an acetyl group, a sulfonyl group, a silyl group, a borane group, a thio group or a seleno group may be mentioned. From the viewpoint of reducing the water absorption of the cured product, an ester group, an alkylcarbonyl group or a silyl group is preferred.

[0081] The content of the epoxy resin (2) in the polycrystal of bisphenol diglycidyl ether is not particularly limited, but is preferably 0 to 10.0% by mass (0% by mass means less than the detection limit), more preferably 0.01 to 10.0% by mass, further preferably 0.1 to 5.0% by mass, and particularly preferably 0.5 to 3.0% by mass, relative to 100% by mass of the polycrystal of bisphenol diglycidyl ether. If the content is at least the lower limit of the above range, a polycrystal of bisphenol diglycidyl ether having excellent solvent solubility can be obtained, while if the content is at most the upper limit of the above range, a polycrystal of bisphenol diglycidyl ether can be obtained in a short time.

[0082] The content of the epoxy resin (2) can be evaluated by the method described in the examples below.

[0083] The polycrystal of bisphenol diglycidyl ether may or may not contain components (other components) other than the above-mentioned epoxy resin (1) and epoxy resin (2) within a range that can achieve the effects of the present invention. Examples of the other components include epoxy resins other than the above-mentioned epoxy resin (1) and epoxy resin (2) (other epoxy resins).

[0084] Examples of other epoxy resins include bisphenol A type epoxy resins, trisphenol methane type epoxy resins, anthracene type epoxy resins, phenol-modified xylene resin type epoxy resins, bisphenol cyclododecyl type epoxy resins, bisphenol diisopropyl resorcinol type epoxy resins, bisphenol F type epoxy resins, bisphenol C type epoxy resins, bisphenol AD type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, dibutyl hydroquinone type epoxy resins, resorcinol type epoxy resins, methyl resorcinol type epoxy resins, bisphenol type epoxy resins, tetramethyl bisphenol type epoxy resins other than the above-mentioned epoxy resins (1) and (2), tetramethyl bisphenol F type epoxy resins, dihydroxydiphenyl ether type epoxy resins, epoxy resins derived from thiobisphenols, dihydroxynaphthalene type epoxy resins, dihydroxyanthracene type epoxy resins, dihydroxydihydroanthracene type epoxy resins, dicyclopentadiene type epoxy resins. Epoxy resins, epoxy resins derived from dihydroxystilbenes, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, naphthol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, terpene phenol-type epoxy resins, dicyclopentadienephenol-type epoxy resins, epoxy resins derived from phenol-hydroxybenzaldehyde condensates, epoxy resins derived from phenol-crotonaldehyde condensates, epoxy resins derived from phenol-glyoxal condensates, epoxy resins derived from co-condensation resins of heavy oils or asphalts, phenols, and formaldehydes, epoxy resins derived from diaminodiphenylmethane, epoxy resins derived from aminophenols, epoxy resins derived from xylenediamine, epoxy resins derived from methylhexahydrophthalic acid, or epoxy resins derived from dimer acid, etc.

[0085] The total content of other components in the polycrystalline form of bisphenol diglycidyl ether is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 15% by mass or less. Furthermore, there is no need to set a lower limit, but the total content may be 0% by mass (less than the detection limit), 1% by mass or more, or 5% by mass or more.

[0086] The melt viscosity of polycrystalline bisphenol diglycidyl ether at 150°C is preferably 1.0 poise or less, more preferably 0.5 poise or less, and even more preferably 0.3 poise or less. When the melt viscosity falls within this range, polycrystalline bisphenol diglycidyl ether can be obtained, shortening the time required to mix raw materials during the production of semiconductor packaging materials. While the lower limit of the melt viscosity is not particularly limited, it is generally 0.01 poise or greater, and may be 0.02 poise or greater, or even 0.05 poise or greater.

[0087] The above-mentioned melt viscosity can be evaluated by the method described in Examples below.

[0088] The epoxy equivalent of the polycrystal of bisphenol diglycidyl ether is not particularly limited, but is preferably 170 g / eq or more, more preferably 174 g / eq or more, and even more preferably 177 g / eq or more. It is preferably 230 g / eq or less, more preferably 220 g / eq or less, and even more preferably 215 g / eq or less.

[0089] If the epoxy equivalent is greater than or equal to the lower limit of the above range, the elastic modulus of the cured product is low, resulting in excellent crack resistance. Furthermore, if the epoxy equivalent is less than or equal to the upper limit of the above range, the Tg of the cured product is high, resulting in excellent heat resistance.

[0090] The epoxy equivalent can be defined as "the mass of an epoxy resin containing one equivalent of epoxy groups" and can be measured in accordance with JIS K7236.

[0091] [Method for producing polycrystalline bisphenol diglycidyl ether]

[0092] The method for producing polycrystals of bisphenol-type diglycidyl ether is not particularly limited. For example, after producing a tetramethylbisphenol-type epoxy resin (hereinafter sometimes referred to as a "crude epoxy resin"), it can be produced using any of the following methods (hereinafter, the following production methods (1) to (3) are sometimes referred to as "production method (1)", "production method (2)" and "production method (3)", respectively).

[0093] (1) The crude epoxy resin is crystallized under desired crystallization conditions.

[0094] (2) After the crude epoxy resin is recrystallized, a crystallization treatment is performed under the desired crystallization conditions.

[0095] (3) After reacting the crude epoxy resin with an alkali metal hydroxide, a crystallization treatment is performed under desired crystallization conditions.

[0096] The method for producing the polycrystal of bisphenol diglycidyl ether after the crude epoxy resin is produced is not particularly limited. From the viewpoint of production efficiency in industrial production, the production method (1) or the production method (2) is preferred, and the production method (1) is more preferred.

[0097] [Manufacturing of crude epoxy resin]

[0098] The method for producing the crude epoxy resin is not particularly limited, and examples thereof include the one-step production method described below.

[0099] <Method for producing crude epoxy resin by one-step method>

[0100] In the one-step method for producing a crude epoxy resin, a crude epoxy resin serving as a raw material for polycrystals of bisphenol-type diglycidyl ether is produced by reacting a bisphenol compound represented by the following formula (3) (hereinafter sometimes referred to as "bisphenol (3)") with an epihalohydrin.

[0101]

[0102] R in the above formula (3) 31 ~R 38 Respectively with R in the above formula (1) 1 ~R 8 Same meaning.

[0103] Examples of the bisphenol (3) include bisphenol, tetramethylbisphenol, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbisphenol, 4,4'-dihydroxy-3,3',5,5'-tetraisopropylbisphenol, and 2,2',6,6'-tetra-tert-butyl-4,4'-dihydroxybisphenol. Bisphenol or tetramethylbisphenol is preferred, and tetramethylbisphenol is particularly preferred.

[0104] When the crude epoxy resin is produced by a one-step process, at least bisphenol (3) and epihalohydrin are used as raw materials, and polyvalent hydroxy compounds other than bisphenol (3) (hereinafter sometimes referred to as "other polyvalent hydroxy compounds") may be used in combination.

[0105] From the perspective of enhancing the effects of the present invention, the proportion of bisphenol (3) is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more relative to the total amount of the polyvalent hydroxy compound used as a raw material. The upper limit is 100 mol%, particularly preferably 100 mol%, but may also be 100 mol% or less, less than 100 mol%, 99.9 mol% or less, 99 mol% or less, or 98 mol% or less. It should be noted that the term "polyvalent hydroxy compound" in this specification refers to a general term for divalent or higher phenolic compounds and divalent or higher alcohols.

[0106] Examples of other polyhydric hydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcinol, methylresorcinol, bisphenol, 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, naphthol novolac resins, brominated bisphenol A, brominated phenol novolac resins, and various polyhydric phenols (excluding bisphenol (3)) obtained by reacting various phenols with benzaldehyde, hydroxybenzaldehyde, and benzophenone. Polyphenol resins obtained by the condensation reaction of various aldehydes such as bean aldehyde or glyoxal, polyphenol resins obtained by the condensation reaction of xylene resin and phenols, various phenolic resins such as co-condensation resins of heavy oil or asphalt, phenols and formaldehyde, chain aliphatic diols such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, and 1,6-hexanediol, cyclic aliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol.

[0107] Preferred polyvalent hydroxy compounds include phenol novolac resins, phenol aralkyl resins, polyvalent phenol resins obtained by a condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resins, naphthol aralkyl resins, chain aliphatic diols such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, or 1,6-hexanediol, cyclic aliphatic diols such as cyclohexanediol or cyclodecanediol, and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, or polypropylene ether glycol.

[0108] The bisphenol (3) used as a raw material and other polyol compounds used as needed are dissolved in an epihalohydrin in an amount of 1.0 to 10.0 equivalents, preferably 2.5 to 8.5 equivalents, and more preferably 4.0 to 7.0 equivalents per equivalent of hydroxyl groups of the total of all polyol compounds to form a uniform solution. If the amount of epihalohydrin is above the lower limit of the above range, it is easy to control the high molecular weight reaction and the epoxy resin obtained can be made into an appropriate epoxy equivalent, which is preferred. On the other hand, if the amount of epihalohydrin is below the upper limit of the above range, there is a trend of improved production efficiency, which is preferred. It should be noted that as the epihalohydrin in this reaction, epichlorohydrin or epibromohydrin are usually used.

[0109] Next, while stirring the solution, an alkali metal hydroxide in an amount of usually 0.5 to 2.0 equivalents, preferably 0.7 to 1.8 equivalents, and more preferably 0.9 to 1.6 equivalents per 1 equivalent of hydroxyl groups of all polyhydroxy compounds of the raw materials is added thereto in the form of a solid or aqueous solution to react. If the amount of the alkali metal hydroxide is above the lower limit of the above range, the unreacted hydroxyl groups are not easy to react with the generated epoxy resin, and it is easy to control the high molecular weight reaction, which is preferred. In addition, if the amount of the alkali metal hydroxide is below the upper limit of the above range, it is not easy to generate impurities caused by side reactions, which is preferred. As the alkali metal hydroxide used here, sodium hydroxide or potassium hydroxide can usually be mentioned.

[0110] The reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is preferably 20 to 150° C., more preferably 40 to 100° C., and even more preferably 40 to 80° C. If the reaction temperature is above the lower limit of the above range, the reaction is easily carried out and the reaction is easily controlled, which is preferred. In addition, if the reaction temperature is below the upper limit of the above range, side reactions are unlikely to proceed, and chlorine impurities are particularly easily reduced, which is preferred.

[0111] The reaction is preferably carried out by dehydrating the following method, that is, while maintaining a specified temperature as needed, the reaction solution is azeotroped, the volatilized steam is cooled, the condensate obtained is subjected to oil / water separation, and the oil content obtained by removing the moisture is returned to the reaction system. In order to suppress the rapid reaction, the alkali metal hydroxide is preferably added intermittently or continuously in a small amount for 0.1 to 8 hours, more preferably 0.1 to 7 hours, and further preferably 0.5 to 6 hours. If the addition time of the alkali metal hydroxide is above the lower limit of the above range, it is possible to prevent the reaction from being violently carried out, and it is easy to control the reaction temperature, thus preferred. In addition, if the addition time is below the upper limit of the above range, it is difficult to generate chlorine impurities, thus preferred, and in addition, from the viewpoint of economic efficiency, it is also preferred. After the reaction is completed, if the insoluble byproduct salt is filtered out and removed, or after being removed by washing with water, unreacted epihalohydrin is removed by reduced pressure distillation, then the target crude epoxy resin can be obtained.

[0112] In addition, in this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, or ethyltriphenylphosphine iodide can be used. wait Salts, or catalysts such as phosphines such as triphenylphosphine.

[0113] In addition, in this reaction, alcohols such as ethanol or isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, diols such as Inert organic solvents include alkanes, ethers such as ethylene glycol dimethyl ether, glycol ethers such as methoxypropanol, dimethyl sulfoxide, and aprotic polar solvents such as dimethylformamide.

[0114] [Production of Polycrystals of Bisphenol-Type Diglycidyl Ether]

[0115] By treating the crude epoxy resin produced as described above using any of the above-mentioned production methods (1) to (3), a polycrystal of bisphenol diglycidyl ether having the above-mentioned crystallization characteristics can be obtained. Furthermore, the crystallization characteristics can be adjusted to an appropriate range by adjusting the crystallization conditions, recrystallization treatment, or reaction conditions with an alkali metal hydroxide. Adjustment of the crystallization conditions, recrystallization treatment, or reaction conditions with an alkali metal hydroxide can be performed individually or in combination.

[0116] That is, for example, by increasing the temperature, the resin content relative to the solvent, or the amount of alkali, the epoxy equivalent can be increased, and conversely, by decreasing the temperature, the resin content relative to the solvent, or the amount of alkali, the epoxy equivalent can be decreased.

[0117] The following describes detailed conditions for producing polycrystalline bisphenol diglycidyl ether. Since the reaction time varies depending on the conditions, appropriate sampling and analysis of the amounts of the various components and epoxy equivalents are performed to obtain the desired polycrystalline bisphenol diglycidyl ether.

[0118] An organic solvent for dissolving the epoxy resin can be used in the reaction of the crude epoxy resin and the alkali metal hydroxide. The organic solvent used in the reaction is not particularly limited, but a mixed solvent of an aprotic polar solvent and an inert organic solvent other than the aprotic polar solvent is preferred from the perspectives of production efficiency, handling properties, and workability.

[0119] As aprotic polar solvent, for example, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, dimethylformamide, dimethylacetamide or hexamethylphosphoramide etc. can be enumerated. These can be used alone or in combination of two or more. Among these aprotic polar solvents, owing to being easy to obtain, the effect is excellent, thereby preferred dimethyl sulfoxide.

[0120] Examples of organic solvents used together with the aprotic polar solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents are preferred due to their effectiveness and ease of post-processing, with methyl isobutyl ketone being particularly preferred. These solvents may be used alone or in combination of two or more.

[0121] The aprotic polar solvent and other organic solvents are preferably used in such a manner that the ratio of the aprotic polar solvent to the total amount thereof is 1 to 30% by mass, particularly 10 to 20% by mass.

[0122] The amount of the organic solvent used is preferably such that the concentration of the crude epoxy resin is generally 3 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 45% by mass.

[0123] Examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide. As the alkali metal hydroxide, it is preferable to use an alkali metal hydroxide dissolved in an organic solvent.

[0124] The amount of alkali metal hydroxide used is preferably 0.01 parts by mass or more and 0.49 parts by mass or less relative to 100 parts by mass of the crude epoxy resin, calculated as the solid content of the alkali metal hydroxide. By adjusting the amount of the alkali metal hydroxide used within this range, the ratio of each component and the epoxy equivalent of the resulting epoxy resin can be easily adjusted to fall within the above-mentioned preferred range. If the amount of the alkali metal hydroxide is outside the above-mentioned range, an epoxy resin containing the epoxy resin (1), the optional epoxy resin (2), and other components within the desired range may not be obtained.

[0125] The reaction temperature of the crude epoxy resin and the alkali metal hydroxide is preferably 40 to 90°C, more preferably 50 to 80°C, and the reaction time is preferably 0.1 to 15 hours, more preferably 0.3 to 12 hours. If the reaction temperature is outside the above range, an epoxy resin containing the desired epoxy resin (1), the optional epoxy resin (2), and other components may not be obtained.

[0126] After the reaction, the excess alkali metal hydroxide and secondary salts are removed by washing with water, and the organic solvent is removed by vacuum distillation and / or steam distillation. The product is then crystallized under desired crystallization conditions to obtain polycrystalline bisphenol diglycidyl ether.

[0127] Regarding the crystallization treatment conditions for obtaining polycrystals of bisphenol diglycidyl ether, it is preferred to use a SUS drum as the container for crystallization. The amount of raw material loaded into the drum is preferably 5 to 20 kg, more preferably 8 to 18 kg, and most preferably 10 to 16 kg. If this loading amount is at least the lower limit of the aforementioned range, the gas content in the drum is low, thus minimizing quality changes during crystallization. If it is at or below the upper limit of the aforementioned range, the loaded material can be easily removed from the drum.

[0128] The holding temperature during crystallization is preferably 8 to 50° C., more preferably 10 to 40° C., and most preferably 15 to 30° C. If the holding temperature is at least the lower limit of the above range, the crystallization time of the content can be shortened, while if it is at most the upper limit of the above range, crystals having a crystallite size within the range specified in this embodiment can be obtained.

[0129] The holding period during crystallization is preferably 0.5 to 40 days, more preferably 1 to 30 days, and most preferably 1.5 to 20 days. If the holding period is greater than the lower limit of the above range, crystals having a crystallite size range specified in the present embodiment can be obtained, while if it is less than the upper limit of the above range, the crystallization time of the contents can be shortened.

[0130] The crystallite size of an organic compound containing an epoxy resin can be adjusted by varying the crystallization rate. Specifically, increasing the crystallization rate yields smaller crystallites, while slowing the crystallization rate yields larger crystallites. The crystallization method for obtaining the polycrystals of the present embodiment described above is characterized in that, by carrying out the crystallization under conditions of slowing the crystallization rate, polycrystals of bisphenol diglycidyl ether having a sufficiently large crystallite size as specified in the present embodiment are obtained.

[0131] Methods for obtaining crystals of organic compounds including epoxy resins include: methods for accelerating the crystallization rate by heating the pre-crystallization molten resin while applying external shear stress, or methods for accelerating crystallization by dissolving the molten resin in a poor solvent for the organic compound and rapidly cooling it for recrystallization. These methods all increase the crystallization rate. On the other hand, as described above, the crystallization method for obtaining the polycrystals of this embodiment is characterized by increasing the crystallite size by slowing the crystallization rate.

[0132] Therefore, in the above-mentioned two methods of increasing the crystallization rate, the crystallite size calculated based on the peak with a specific diffraction angle (2θ) in the powder X-ray diffraction pattern measured by CuKα rays is smaller than the crystallite size specified in this embodiment, and therefore crystals having the crystallite size range specified in this embodiment cannot be obtained.

[0133] [Resin composition containing polycrystals of bisphenol-type diglycidyl ether]

[0134] The resin composition of another embodiment of the present invention is a polycrystalline resin composition containing the above-mentioned bisphenol diglycidyl ether, preferably a resin composition further appropriately formulated with a curing agent, other epoxy resins other than the above-mentioned epoxy resin (hereinafter sometimes referred to as "other epoxy resins"), a curing accelerator, an inorganic filler, a release agent or a coupling agent, etc., as needed, and it is particularly preferred that the resin composition contains a curing agent.

[0135] [Curing agent]

[0136] In this specification, a curing agent refers to a substance that facilitates the crosslinking reaction and / or chain extension reaction between epoxy groups in an epoxy resin. In this specification, even substances referred to as "curing accelerators" are generally considered curing agents as long as they facilitate the crosslinking reaction and / or chain extension reaction between epoxy groups in an epoxy resin.

[0137] The content of the curing agent in the resin composition containing the polycrystal of bisphenol diglycidyl ether is not particularly limited, but is preferably 0.01 to 1000 parts by mass, more preferably 0.1 to 1000 parts by mass, further preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less, relative to 100 parts by mass of all epoxy resin components as solid content.

[0138] In this specification, "solid content" refers to the component obtained by removing the solvent, and as a property, it includes not only solid epoxy resin but also semi-solid and viscous liquid substances. "Total epoxy resin content" corresponds to the amount of epoxy resin contained in the resin composition containing polycrystals of bisphenol-type diglycidyl ether. When the resin composition containing polycrystals of bisphenol-type diglycidyl ether contains only polycrystals of bisphenol-type diglycidyl ether, it corresponds to the amount of epoxy resin (epoxy resin (1), epoxy resin (2) as an optional component, and epoxy resins in other components) in the polycrystals of bisphenol-type diglycidyl ether. When the resin composition containing polycrystals of bisphenol-type diglycidyl ether contains polycrystals of bisphenol-type diglycidyl ether and other epoxy resins, the total epoxy resin content corresponds to the total amount of epoxy resin in the polycrystals of bisphenol-type diglycidyl ether and other epoxy resins.

[0139] The curing agent is not particularly limited, and any of those generally known as epoxy resin curing agents can be used. For example, phenolic curing agents, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, or imidazoles can be mentioned. Preferably, at least one curing agent is selected from the group consisting of phenolic curing agents, amine curing agents, acid anhydride curing agents, and amide curing agents.

[0140] Among them, by containing a phenolic curing agent, the resin composition containing polycrystals of bisphenol-type diglycidyl ether can obtain excellent heat resistance, stress resistance, water absorption resistance, and flame retardancy. Therefore, as a curing agent, it is preferable to contain a phenolic curing agent. From the perspective of heat resistance, it is preferable to contain an anhydride curing agent or an amide curing agent. From the perspective of increasing the glass transition temperature of the resin composition containing polycrystals of bisphenol-type diglycidyl ether, it is preferable to contain an amine curing agent. From the perspective of ensuring that the curing reaction proceeds sufficiently and improving heat resistance, it is also preferable to use an imidazole.

[0141] The curing agent may be used alone or in combination of two or more. When two or more curing agents are used in combination, they may be mixed in advance to prepare a mixed curing agent before use, or the curing agent components may be added separately when mixing the components of the resin composition containing the polycrystalline bisphenol diglycidyl ether and mixed simultaneously.

[0142] <Phenolic curing agent>

[0143] Specific examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, bisphenol, tetramethylbisphenol, 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, brominated phenol novolac resins, and various polyphenols, or Polyphenol resins obtained by the condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, or glyoxal; polyphenol resins obtained by the condensation reaction of xylene resin and phenols; co-condensation resins of heavy oil or asphalt with phenols and formaldehydes; or various phenolic resins such as phenol·benzaldehyde·benzyl dimethoxide condensation product, phenol·benzaldehyde·benzyl dihalide condensation product, phenol·benzaldehyde·4,4'-dimethoxybiphenyl condensation product, or phenol·benzaldehyde·4,4'-dihalide biphenyl condensation product.

[0144] The phenolic curing agent may be used alone or in combination of two or more in any combination and mixing ratio.

[0145] Among the above-mentioned phenolic curing agents, phenol novolac resins (e.g., compounds represented by the following formula (7)), phenol aralkyl resins (e.g., compounds represented by the following formula (8)), biphenyl aralkyl resins (e.g., compounds represented by the following formula (9)), naphthol novolac resins (e.g., compounds represented by the following formula (10)), naphthol aralkyl resins (e.g., compounds represented by the following formula (11)), trisphenol methane type resins (e.g., compounds represented by the following formula (12)), and phenolic aralkyl resins (e.g., compounds represented by the following formula (13)) are preferred from the viewpoints of heat resistance and curability of the composition after curing. Such as the compound represented by the following formula (12)), phenol·benzaldehyde·benzyl dimethylol condensation product (for example, the compound represented by the following formula (13)), phenol·benzaldehyde·benzyl dimethyl dihalide condensation product (for example, the compound represented by the following formula (13)), phenol·benzaldehyde·4,4'-dimethoxybiphenyl condensation product (for example, the compound represented by the following formula (14)), or phenol·benzaldehyde·4,4'-dihalide biphenyl condensation product (for example, the compound represented by the following formula (14)), etc.

[0146] Among them, particularly preferred are phenol novolac resins (e.g., compounds represented by the following formula (7)), phenol aralkyl resins (e.g., compounds represented by the following formula (8)), biphenyl aralkyl resins (e.g., compounds represented by the following formula (9)), phenol-benzaldehyde-xylylenedimethoxide polycondensates (e.g., compounds represented by the following formula (13)), phenol-benzaldehyde-xylylenedimethoxide polycondensates (e.g., compounds represented by the following formula (13)), phenol-benzaldehyde-xylylenedimethoxide polycondensates (e.g., compounds represented by the following formula (13)), phenol-benzaldehyde-4,4'-dimethoxybiphenyl polycondensates (e.g., compounds represented by the following formula (14)), and phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensates (e.g., compounds represented by the following formula (14)).

[0147]

[0148] In the above formulae (7) to (12), k1 to k6 each independently represent a number of 0 or greater, and may be 10 or less, or 5 or less.

[0149]

[0150] In the above formulae (13) and (14), k7, k8, l1, and l2 each independently represent a number greater than or equal to 1, and may be less than or equal to 10 or less than or equal to 5.

[0151] The amount of the phenolic curing agent incorporated is preferably 0.1 to 1000 parts by mass, more preferably 500 parts by mass or less, even more preferably 300 parts by mass or less, and particularly preferably 100 parts by mass or less, relative to 100 parts by mass of the total epoxy resin component in the resin composition containing the polycrystal of bisphenol-type diglycidyl ether. An amount within this range is preferred because unreacted epoxy groups and functional groups of the curing agent are less likely to remain.

[0152] <Amine curing agent>

[0153] Examples of the amine-based curing agent (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines.

[0154] Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, N-hydroxyethylethylenediamine, and tetrakis(hydroxyethyl)ethylenediamine.

[0155] Examples of the polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamine.

[0156] Examples of the alicyclic amines include isophoronediamine, diamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane or norbornene diamine, etc.

[0157] Examples of the aromatic amines include tetrachloro-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 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'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[0158] The amine-based curing agent may be used alone or in combination of two or more in any combination and mixing ratio.

[0159] The amount of the amine curing agent incorporated is preferably in the range of 0.8 to 1.5, as measured by the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all epoxy resin components contained in the resin composition comprising polycrystalline bisphenol diglycidyl ether. Amounts within this range are preferred because unreacted epoxy groups and functional groups of the curing agent are less likely to remain.

[0160] <Tertiary amine>

[0161] Examples of the tertiary amine include 1,8-diazabicyclo(5,4,0)undec-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol.

[0162] The tertiary amine may be used alone or in combination of two or more in any combination and mixing ratio.

[0163] The amount of the tertiary amine incorporated is preferably in the range of 0.8 to 1.5, as measured by the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all epoxy resin components contained in the resin composition comprising the polycrystals of bisphenol-type diglycidyl ether. Amounts within this range are preferred because unreacted epoxy groups and functional groups in the curing agent are less likely to remain.

[0164] <Anhydride-based curing agent>

[0165] Examples of the acid anhydride-based curing agent include acid anhydrides and modified products of acid anhydrides.

[0166] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, Formic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bis(trimellitate) dianhydride, chlorobridged anhydride, nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride or 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc.

[0167] As modified products of acid anhydrides, for example, modified products obtained by modifying the above-mentioned acid anhydrides with glycols can be mentioned. Here, as examples of glycols that can be used for modification, alkylene glycols such as ethylene glycol, propylene glycol, or neopentyl glycol, or polyether glycols such as polyethylene glycol, polypropylene glycol, or polytetramethylene ether glycol can be mentioned. In addition, copolyether glycols of two or more glycols and / or polyether glycols among these can also be used.

[0168] In the modified product of anhydride, it is preferred to modify with 0.4 mol or less of diol per mol of anhydride. If the modification amount is below the upper limit of the above range, the viscosity of the epoxy resin composition will not become too high, and there is a tendency for good workability. In addition, there is a tendency for the speed of the curing reaction with the epoxy resin to become good.

[0169] The acid anhydride curing agent may be used alone or in combination of two or more in any combination and in any amount.

[0170] When an acid anhydride curing agent is used, the amount of the acid anhydride curing agent blended is preferably in the range of 0.8 to 1.5, as measured by the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all epoxy resin components in the resin composition containing the polycrystals of bisphenol diglycidyl ether. A blending amount within this range is preferred because unreacted epoxy groups and functional groups of the curing agent are less likely to remain.

[0171] <Amide-based curing agent>

[0172] Examples of the amide curing agent include dicyandiamide or derivatives thereof, and polyamide resins, etc. The amide curing agent may be used alone or in combination of two or more in any ratio.

[0173] When an amide curing agent is used, the amount of the amide curing agent incorporated is preferably 0.1 to 20% by mass relative to the total amount of the epoxy resin component and the amide curing agent in the resin composition containing the polycrystal of bisphenol diglycidyl ether. When the amount is within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferred.

[0174] Imidazoles

[0175] Examples of the imidazoles 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, and 1-cyanoethyl-2-phenylimidazole. Trimellitate, 2,4-diamino-6-[2'-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, or adducts of epoxy resins and the above imidazoles, etc.

[0176] Imidazoles are generally classified as curing accelerators due to their catalytic ability, but are classified as curing agents in this specification.

[0177] The imidazoles may be used alone or in combination of two or more in any ratio.

[0178] When imidazoles are used, the amount of imidazoles blended is preferably 0.1 to 20% by mass relative to the total amount of all epoxy resin components and imidazoles in the resin composition containing the polycrystal of bisphenol diglycidyl ether. If the blending amount is within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferred.

[0179] <Other curing agents>

[0180] In the resin composition containing the polycrystal of bisphenol diglycidyl ether, other curing agents may be used in addition to the above-mentioned curing agents. The other curing agents are not particularly limited, and any of those generally known as curing agents for epoxy resins can be used.

[0181] Other curing agents may be used alone or in combination of two or more.

[0182] [Other epoxy resins]

[0183] The resin composition containing the polycrystals of bisphenol diglycidyl ether may further contain other epoxy resins in addition to the polycrystals of bisphenol diglycidyl ether described above. By containing other epoxy resins, the heat resistance, stress resistance, water absorption resistance, flame retardancy, etc. of the resin composition can be improved.

[0184] Other epoxy resins that can be used in the resin composition containing the polycrystal of bisphenol-type diglycidyl ether include all epoxy resins other than the above-mentioned epoxy resins (epoxy resin (1) and epoxy resin (2) as an optional component).

[0185] Specific examples of other epoxy resins include bisphenol A type epoxy resin, trisphenol methane type epoxy resin, anthracene type epoxy resin, phenol-modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropyl resorcinol type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, bisphenol type epoxy resin, tetramethyl bisphenol type epoxy resin other than the above-mentioned epoxy resins (1) and (2), tetramethyl bisphenol F type epoxy resin, dihydroxy diphenyl ether type epoxy resin, epoxy resin derived from thiobisphenols, dihydroxy naphthalene type epoxy resin, dihydroxy anthracene type epoxy resin, dihydroxy dihydroanthracene type epoxy resin, and dicyclopentadiene type epoxy resin. , epoxy resins derived from dihydroxystilbene, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, terpene phenol type epoxy resins, dicyclopentadiene phenol type epoxy resins, epoxy resins derived from phenol-hydroxybenzaldehyde condensates, epoxy resins derived from phenol-crotonaldehyde condensates, epoxy resins derived from phenol-glyoxal condensates, epoxy resins derived from co-condensation resins of heavy oil or asphalt with phenols and formaldehydes, epoxy resins derived from diaminodiphenylmethane, epoxy resins derived from aminophenol, epoxy resins derived from xylenediamine, epoxy resins derived from methylhexahydrophthalic acid, or epoxy resins derived from dimer acid, etc.

[0186] These may be used alone or in any combination and at any mixing ratio.

[0187] Among the above-mentioned other epoxy resins, bisphenol A type epoxy resin, tetramethylbisphenol type epoxy resin other than the above-mentioned epoxy resins (1) and (2), 4,4'-bisphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, dihydroxyanthracene type epoxy resin, dicyclopentadiene type epoxy resin, o-cresol novolac type epoxy resin, or trisphenol methane type epoxy resin is particularly preferred from the viewpoints of the fluidity of the composition and the heat resistance, water absorption resistance, flame retardancy, etc. of the cured product.

[0188] When the resin composition containing the polycrystal of bisphenol diglycidyl ether contains the above-mentioned other epoxy resin, the content thereof is preferably 0.01 to 60 parts by mass, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and more preferably 1 part by mass or more, relative to 100 parts by mass of all epoxy resin components in the composition.

[0189] [Curing accelerator]

[0190] The resin composition containing the polycrystal of bisphenol diglycidyl ether preferably contains a curing accelerator. By containing a curing accelerator, the curing time can be shortened, the curing temperature can be lowered, and the desired cured product can be easily obtained.

[0191] The curing accelerator is not particularly limited, and specific examples thereof include organic phosphines, Phosphorus compounds such as salts, tetraphenylborate salts, organic acid dihydrazides, or boron halide amine complexes.

[0192] Examples of phosphorus compounds that can be used as curing accelerators include organic phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl / alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, or alkyldiarylphosphine; complexes of these organic phosphines with organic boron; or compounds obtained by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone; or compounds such as diazoniumphenylmethane.

[0193] Among the curing accelerators mentioned above, organic phosphines or Salts, most preferably organic phosphines.

[0194] As the curing accelerator, only one of the curing accelerators listed above may be used, or two or more of them may be mixed in any combination and ratio and used.

[0195] The content of the curing accelerator is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of all epoxy resin components in the resin composition containing the polycrystalline bisphenol diglycidyl ether. Furthermore, it is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. If the content of the curing accelerator is at least the lower limit of the above range, a good curing acceleration effect can be achieved. If the content of the curing accelerator is at most the upper limit of the above range, the desired cured physical properties are easily achieved, which is preferred.

[0196] [Inorganic fillers]

[0197] In the polycrystalline resin composition comprising bisphenol type diglycidyl ether, inorganic filling material can be coordinated. As inorganic filling material, for example, fused silica, crystalline silica, glass powder, aluminum oxide, calcium carbonate, calcium sulfate, talc or boron nitride etc. can be enumerated. These can only use one kind, and can also use two or more kinds in any combination and proportion combination. Among these, in the case of the purposes for semiconductor sealing, preferably crushed type and / or spherical melting and / or crystalline silica powder filling material.

[0198] By using an inorganic filler, when a resin composition containing polycrystalline bisphenol diglycidyl ether is used as a semiconductor packaging material, the thermal expansion coefficient of the semiconductor packaging material can be brought closer to that of the silicon chip and lead frame within. Furthermore, the overall water absorption of the semiconductor packaging material can be reduced, thereby improving solder crack resistance.

[0199] The average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, and more preferably 2 to 30 μm. An average particle size equal to or greater than the lower limit of the above range is preferred because the melt viscosity does not become too high and the fluidity is less likely to decrease.

[0200] When the average particle size of the inorganic filler is equal to or smaller than the upper limit of the above range, the filler is less likely to clog a narrow gap in a mold during molding, and the filling property of the material is easily improved, which is preferred.

[0201] When an inorganic filler is used in the resin composition containing the polycrystal of bisphenol diglycidyl ether, the amount of the inorganic filler added to the epoxy resin composition is preferably 60 to 95% by mass.

[0202] [Release agent]

[0203] A release agent may be added to the polycrystalline resin composition containing bisphenol diglycidyl ether. Examples of release agents include natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid or zinc stearate, or their metal salts, or hydrocarbon-based release agents such as paraffin wax. These may be used alone or in combination of two or more in any desired combination and ratio.

[0204] When a release agent is added to a resin composition containing polycrystalline bisphenol diglycidyl ether, the amount of the release agent added is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, relative to 100 parts by mass of all epoxy resin components in the resin composition. When the amount of the release agent is within this range, the curing characteristics of the resin composition are maintained while exhibiting good releasability, which is preferred.

[0205] [Coupling agent]

[0206] A coupling agent is preferably added to the resin composition containing the polycrystal of bisphenol diglycidyl ether. The coupling agent is preferably used in combination with an inorganic filler. The addition of a coupling agent can improve the adhesion between the epoxy resin serving as the matrix and the inorganic filler. Examples of coupling agents include silane coupling agents and titanate coupling agents.

[0207] Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino silanes such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, or γ-ureidopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinyl silanes such as p-phenylyltrimethoxysilane; vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, or γ-methacryloxypropyltrimethoxysilane; and epoxy-, amino-, or vinyl-based polymeric silanes.

[0208] Examples of the titanate coupling agent include triisostearoyl isopropyl titanate, tris(N-aminoethyl / aminoethyl) isopropyl titanate, diisopropyl bis(dioctylphosphoyloxy) titanate, tetraisopropyl bis(dioctylphosphiteoxy) titanate, tetraoctyl bis(ditridecylphosphiteoxy) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl pyrophosphateoxy)oxyacetate titanate, and bis(dioctyl pyrophosphateoxy)ethylene titanate.

[0209] These coupling agents may be used alone or in combination of two or more in any ratio.

[0210] When a coupling agent is used in a resin composition containing polycrystalline bisphenol diglycidyl ether, the amount of coupling agent added is preferably 0.1 to 3.0 parts by mass relative to 100 parts by mass of the total epoxy resin component. If the amount of coupling agent added is at least the lower limit of the above range, the addition of the coupling agent tends to enhance the adhesion between the epoxy resin serving as the matrix and the inorganic filler. If the amount of coupling agent added is at most the upper limit of the above range, the coupling agent is less likely to ooze out of the resulting cured product, which is preferred.

[0211] [Other ingredients]

[0212] In the resin composition containing the polycrystal of bisphenol diglycidyl ether, components other than the above components (sometimes referred to as "other components" in this specification) can be mixed. As other components, for example, flame retardants, plasticizers, reactive diluents, or pigments can be cited. These can be appropriately mixed as needed within the scope of obtaining the effects of the present invention. In addition to the above components listed as other components, substances other than the above components can be mixed in the resin composition.

[0213] Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resins and brominated phenolic resins, antimony compounds such as antimony trioxide, phosphorus-based flame retardants such as red phosphorus, phosphates, and phosphines, nitrogen-based flame retardants such as melamine derivatives, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0214] [cured material]

[0215] The method for curing the resin composition containing the polycrystal of bisphenol diglycidyl ether is not particularly limited.

[0216] The cured product of another embodiment of the present invention is a cured product of a resin composition containing a polycrystal of bisphenol-type diglycidyl ether, which can usually be obtained by curing the above-mentioned resin composition through a heat curing reaction caused by heating. During the heat curing reaction, it is preferred to appropriately select the curing temperature according to the type of curing agent used. For example, when a phenolic curing agent is used, the curing temperature is usually 130 to 300°C. By adding a curing accelerator to these curing agents, the curing temperature can also be lowered. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and further preferably 3 to 15 hours. If the reaction time is above the lower limit of the above range, there is a tendency for the curing reaction to proceed sufficiently, and thus it is preferred. If the reaction time is below the upper limit of the above range, it is easy to reduce the deterioration caused by heating and the energy loss during heating, and thus it is preferred.

[0217] [use]

[0218] A cured product of a resin composition containing a polycrystal of bisphenol diglycidyl ether has low water absorption, is excellent in heat crack resistance during molding and in electrical reliability during long-term use, and can therefore be preferably used as an electrical or electronic material.

[0219] The resin composition containing the polycrystal of bisphenol diglycidyl ether and its cured product can be appropriately included in the above-mentioned electrical and electronic materials for use, but as long as the application requires the above-mentioned physical properties, it can be effectively used in any application. For example, the resin composition and its cured product can be appropriately included in the following fields for use, that is, optical fields such as optical materials; coating fields such as automotive coatings such as automotive electroplating coatings, heavy-duty anti-corrosion coatings for ships and bridges, or coatings for the inner surface coating of beverage cans; electrical and electronic fields such as composite materials, laminated boards, semiconductor packaging materials, liquid insulation packaging materials, insulating powder coatings, or coil impregnation materials; seismic reinforcement materials for bridges, concrete reinforcement materials, floor materials for buildings, lining materials for water supply facilities, drainage and permeable paving materials, structural, vehicle, and aircraft adhesives, and other fields. Among these, the resin composition and its cured product can be particularly preferably included in the electrical and electronic fields for use, and specifically, it is useful as electrical and electronic components.

[0220] When a cured product of a polycrystalline resin composition containing bisphenol diglycidyl ether is used in the above-mentioned applications, the cured product may be used as a material for the above-mentioned applications or may be cured and used in the production process for the above-mentioned applications.

[0221] [Laminated board]

[0222] As a method for producing a laminate using a resin composition containing polycrystalline bisphenol diglycidyl ether, there is exemplified a method in which a laminate including a prepreg is heated and pressurized to cure the laminate, wherein the prepreg is obtained by impregnating a fibrous base material with a resin varnish composed of a resin composition containing polycrystalline bisphenol diglycidyl ether.

[0223] More specifically, a fibrous substrate is impregnated with a resin varnish and dried to remove the solvent to form a prepreg. This prepreg can be laminated with other substrates as needed to form a laminate, which can then be cured by heating and pressurizing to form a laminate.

[0224] The number of layers of the prepreg in the laminate can be 1 layer or more than 2 layers. In the laminate, other substrates other than the prepreg can be stacked. As other substrates, for example, metal foils such as copper foil can be mentioned.

[0225] Examples of the fibers constituting the fibrous substrate include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, or stainless steel fibers; natural fibers such as cotton, linen, or paper; and synthetic organic fibers such as polyester resins or polyamide resins. These fibers may be used alone or in combination of two or more.

[0226] The shape of the fibrous substrate is not particularly limited, and examples thereof include short fibers, spun yarns, felts, and sheets.

[0227] The amount of the resin varnish to be impregnated into the fibrous substrate is not particularly limited. For example, the solid content of the resin varnish to be impregnated is about 30 to 50 parts by mass based on 100 parts by mass of the fibrous substrate.

[0228] The heating temperature when the laminate is heated and pressurized is preferably the curing temperature of the above-mentioned resin composition. As the pressurizing conditions, 2 to 20 kN / m 2 .

[0229] The laminate thus manufactured comprises a fiber-reinforced resin layer comprising a fibrous base material and a cured product of a resin varnish. The number of fiber-reinforced resin layers in the laminate may be one or more. As described above, the laminate may comprise a metal foil layer such as copper foil.

[0230] [Packaging materials]

[0231] When a resin composition containing polycrystalline bisphenol diglycidyl ether is used as a packaging material, the shape of the packaging material to which the resin composition is applied is not particularly limited. For example, the same shape as that used for known semiconductors can be used.

[0232] As a method for forming a sealing material using a resin composition containing a polycrystal of bisphenol diglycidyl ether, for example, a transfer molding method or a compression molding method can be used.

[0233] Example

[0234] The present invention will be described in more detail below based on the examples. The present invention is not limited in any way by the following examples. The values of the various manufacturing conditions and evaluation results in the following examples have the meaning of preferred values as upper or lower limits in the embodiments of the present invention, and the preferred range can be a range defined by a combination of the values of the above upper or lower limits and the values of the following examples, or the values of the examples themselves.

[0235] [Raw materials used, etc.]

[0236] The structural formulas of raw materials, reaction products, etc. used in the following Examples and Comparative Examples are as follows.

[0237] Epoxy resin (1-1)

[0238]

[0239] Epoxy resin (2-1)

[0240]

[0241] Tetramethylbisphenol (3-1) (Mitsubishi Chemical Corporation)

[0242]

[0243] [Measurement and evaluation methods]

[0244] The measurement and evaluation methods of the physical properties of the polycrystals or epoxy resins obtained in the following Examples and Comparative Examples are as follows.

[0245] <Epoxy equivalent>

[0246] The epoxy equivalent of the polycrystal is defined as "the mass of the epoxy resin containing one equivalent of epoxy groups" and is measured in accordance with JIS K7236.

[0247] <Powder X-ray Diffraction (XRD)>

[0248] XRD measurement of the powder sample was performed using an X'Pert Pro MPD manufactured by PANalytical using CuKα rays with a focused optical system.

[0249] Using the XRD analysis software JADE Pro, for each of the following regions, a straight line connecting both ends was removed as background, and then profile fitting was performed to derive the diffraction peak angle (2θ) and half-value width (β).

[0250] Peak 1: 8.9°~9.3°, Peak 2: 15.1°~15.5°, Peak 3: 19.4°~19.8°, Peak 4: 24.9°~25.3°

[0251] The crystallite size was calculated from the following formula (A) (Scherrer's formula) using the half-value width β obtained by correcting the broadening of the peak originating from the device.

[0252] D=Kλ / βcosθ(A)

[0253] In (Formula A), each symbol is as follows.

[0254] D: Crystallite size

[0255] K: Scherrer constant K = 0.9

[0256] λ: wavelength of X-rays

[0257] β: Full width at half maximum (rad)

[0258] θ: Bragg angle (rad)

[0259] Here, β uses the measured half-height width β0, the half-height width β from the device, and i Calculated by the following formula (B). i The full width at half maximum calculated from the diffraction pattern of Si powder (NIST640c) was used.

[0260] β 2 =β0 2 -β i 2 (B)

[0261] <Composition of polycrystalline bisphenol diglycidyl ether>

[0262] The content ratio of the epoxy resins (1-1) and (2-1) in the polycrystals of bisphenol diglycidyl ether was calculated as the ratio (mass %) obtained by dividing the area % of each region of the LC spectrum representing the epoxy resin (1-1), the epoxy resin (2-1), and other components by the total area % of the epoxy resin (1-1), the epoxy resin (2-1), and other components by LC analysis performed using the following apparatus and conditions in accordance with JIS K0124.

[0263] Apparatus: Waters 2690 high performance liquid chromatograph manufactured by Waters Corporation Column: TSKgel ODS-120A manufactured by Tosoh Corporation (column size: 4.6 mm ID × 15 cm)

[0264] Eluent: After 60 minutes, acetonitrile / water = 30 / 70 becomes 100 / 0

[0265] Gradient analysis flow rate: 1 mL / min

[0266] Detector: UV (280nm)

[0267] Temperature: 35℃

[0268] Sample concentration: 0.1%

[0269] Injection volume: 10 μL

[0270] Peak area analysis software: Empower2 manufactured by Waters

[0271] Melting point

[0272] The melting point of the polycrystal was measured using a differential scanning calorimeter (manufactured by Hitachi High-Technologies). The melting point was determined as the temperature at the endothermic peak when the temperature of a 5 mg sample was increased at 10°C / min. In cases where multiple peaks were observed, the temperatures at the endothermic peaks, starting from the lower temperature, are reported in Table 1.

[0273] <Measurement of melt viscosity>

[0274] Polycrystals of bisphenol diglycidyl ether were melted on a hot plate of a cone-plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150° C., and the melt viscosity (Poise) was measured at a rotation speed of 750 rpm.

[0275] <Evaluation of crystallization days>

[0276] As shown in the Examples and Comparative Examples described below, epoxy resin crystallization was performed in an 18L drum. The number of days required to obtain polycrystals is shown in Table 1 as the crystallization days. Crystallization days of 45 days or less were considered to indicate that polycrystals could be obtained in a short period of time. While the crystallization process (maintaining the temperature at 20°C) in the Examples and Comparative Examples was performed for 60 days, the crystallization days shown in Table 1 are the days required to obtain polycrystals.

[0277] <Crushing>

[0278] The polycrystals of bisphenol diglycidyl ether obtained by crystallization in an 18 L drum in the evaluation of the number of days for crystallization described above were extracted from the 18 L drum and pulverized using a pulverizer (Feather Mill FM-2 manufactured by Hosokawa Micron Co., Ltd.). The pulverizability was evaluated according to the following criteria.

[0279] The case where no sticking was observed in the device during pulverization was evaluated as "A".

[0280] The case where sticking was observed in the apparatus during pulverization or the case where no crystals were obtained and pulverization could not be performed was evaluated as "B".

[0281] <Particle size measurement>

[0282] The pulverized product obtained by the above pulverization treatment was measured for particle size, and the average particle size (μm), D10 (μm), D50 (μm), and D90 (μm) were calculated. Particle sizes less than 50 μm were measured using a laser scattering method (apparatus: Microtrac BEL 3000EXII, dispersion medium: water). Particle sizes greater than 50 μm were measured using a sieving method (apparatus: Tsutsui Rikagaku Co., Ltd. MicroVibro Sifter M-3T, sieve openings: 32, 63, 125, 250, 500, 1000, 2000, and 4000 μm, vibration conditions: vibration intensity 5 for 2 minutes).

[0283] Parameters related to particle size were measured only in Examples 1 to 4.

[0284] [Production and Evaluation of Polycrystalline Bisphenol Diglycidyl Ether]

[0285] [Manufacturing Example]

[0286] Into a 10L autoclave equipped with a thermometer, a stirring device and a cooling tube, 900g of the raw material phenol, i.e., tetramethylbisphenol (3-1) (manufactured by Mitsubishi Chemical Corporation), 4473g of epichlorohydrin, 1741g of isopropyl alcohol and 462g of water were added. After heating to 40°C to dissolve them uniformly, 713g of a 48.5% by mass sodium hydroxide aqueous solution was added dropwise over 90 minutes. While adding dropwise, the temperature was raised from 40°C to 65°C over 90 minutes. Then, the reaction was completed by maintaining it at 65°C for 30 minutes, and 1340g of warm water at 65°C was added to dissolve the by-product salts and excess sodium hydroxide. The mixture was allowed to stand at 65°C for 1 hour. After standing, the water layer was extracted from the separated oil layer and water layer. Then, the epichlorohydrin was completely removed under reduced pressure at 150°C to obtain a crude epoxy resin.

[0287] Then, 1974 g of methyl isobutyl ketone was added, and the temperature was raised to 65°C to allow uniform dissolution. Then, 28 g of a 48.5% by mass sodium hydroxide aqueous solution was added, and the mixture was reacted for 60 minutes. The mixture was then washed four times with 2000 g of water. The methyl isobutyl ketone was then completely removed under reduced pressure at 150°C to obtain an epoxy resin.

[0288] [Example 1]

[0289] An epoxy resin was obtained by the same operation as in the above-mentioned manufacturing example. The obtained epoxy resin was then crystallized three times in propylene glycol monomethyl ether. The above operation was repeated until 10 kg of epoxy resin was obtained. Then, propylene glycol monomethyl ether was completely removed under reduced pressure at 150°C, and a predetermined amount was filled into an 18 L drum. After heating at 150°C for 6 hours, crystallization was carried out at 20°C for 60 days to obtain a polycrystal of bisphenol-type diglycidyl ether of Example 1 (manufacturing method (2)). The epoxy resin filled into the drum was evaluated for the number of days it took to crystallize a polycrystal using the above-mentioned method. The above-mentioned measurements and evaluations were performed using this polycrystal.

[0290] Table 1 shows the results.

[0291] [Example 2]

[0292] The same operation as in the above-mentioned production example was repeated several times until 10 kg of epoxy resin was obtained. The epoxy resin obtained was filled into an 18 L drum in a predetermined amount, heated at 150°C for 6 hours, and then crystallized at 20°C for 60 days to obtain a polycrystal of bisphenol-type diglycidyl ether of Example 2 (Production Method (1)). The epoxy resin filled into the drum was evaluated for the number of days it took to crystallize a polycrystal using the above-mentioned method. The polycrystal was used to perform the above-mentioned measurements and evaluations.

[0293] Table 1 shows the results.

[0294] [Example 3]

[0295] An epoxy resin was obtained by the same operation as in the above-mentioned production example. Then, 2500 g of the obtained epoxy resin, 3000 g of methyl isobutyl ketone and 750 g of dimethyl sulfoxide were added to a 10 L autoclave equipped with a thermometer, a stirring device and a cooling tube. After the reaction temperature was raised to 65°C to allow uniform dissolution, 123 g of an 8% by mass potassium hydroxide / isopropanol solution was added and the reaction was carried out for 1.5 hours. Then, 750 g of methyl isobutyl ketone was added and the mixture was washed four times with 1000 g of water. Then, the mixture was washed four times with 1000 g of water. Then, the methyl isobutyl ketone was completely removed under reduced pressure at 150°C to obtain an epoxy resin. The above operation was repeated until 10 kg of epoxy resin was obtained. Then, the obtained epoxy resin was filled into an 18 L drum in a specified amount, heated at 150°C for 6 hours, and then crystallized at 20°C for 60 days to obtain a polycrystalline bisphenol diglycidyl ether of Example 3 (production method (3)). The epoxy resin filled in the barrel was evaluated for the number of days it took for a polycrystal to be crystallized by the above method. The above-mentioned measurements and evaluations were performed using the polycrystal.

[0296] Table 1 shows the results.

[0297] [Example 4]

[0298] An epoxy resin was obtained by the same operation as in the above-mentioned manufacturing example. Then, 2500 g of the obtained epoxy resin, 3000 g of methyl isobutyl ketone and 750 g of dimethyl sulfoxide were added to a 10 L autoclave equipped with a thermometer, a stirring device and a cooling tube. After the reaction temperature was raised to 65°C to allow uniform dissolution, 123 g of an 8% by mass potassium hydroxide / isopropanol solution was added and the reaction was carried out for 2 hours. Then, 750 g of methyl isobutyl ketone was added and the mixture was washed four times with 1000 g of water. Then, the methyl isobutyl ketone was completely removed under reduced pressure at 150°C to obtain an epoxy resin. The above operation was repeated several times until 10 kg of epoxy resin was obtained. Then, the obtained epoxy resin was filled into an 18 L drum in a specified amount, heated at 150°C for 6 hours, and then crystallized at 20°C for 60 days to obtain a polycrystalline bisphenol diglycidyl ether of Example 4 (manufacturing method (3)). The epoxy resin filled in the barrel was evaluated for the number of days it took for a polycrystal to be crystallized by the above method. The above-mentioned measurements and evaluations were performed using the polycrystal.

[0299] Table 1 shows the results.

[0300] [Comparative Example 1]

[0301] An epoxy resin was obtained by the same procedures as in the above-mentioned preparation example. Subsequently, 2500 g of the obtained epoxy resin, 3000 g of methyl isobutyl ketone, and 750 g of dimethyl sulfoxide were placed in a 10 L autoclave equipped with a thermometer, a stirrer, and a cooling tube. The reaction temperature was raised to 65°C for uniform dissolution. Then, 246 g of an 8% by mass potassium hydroxide / isopropyl alcohol solution was added and the reaction was allowed to proceed for 1 hour. Subsequently, 750 g of methyl isobutyl ketone was added, and the mixture was washed four times with 1000 g of water. The methyl isobutyl ketone was then completely removed under reduced pressure at 150°C to obtain an epoxy resin composition. This procedure was repeated until 10 kg of epoxy resin was obtained. The prescribed amount of the obtained epoxy resin was then filled into an 18 L drum, heated at 150°C for 6 hours, and then crystallized at 20°C for 60 days to obtain a polycrystal of bisphenol diglycidyl ether of Example 4. The epoxy resin filled into the drum was evaluated for the number of days it took for the polycrystal to be crystallized using the above method. Using this polycrystal, the above-mentioned measurements and evaluations were performed.

[0302] Table 1 shows the results.

[0303] [Comparative Example 2]

[0304] The same procedures as in Comparative Example 1 were followed, except that the crystallization conditions in an 18L drum were changed from "20°C for 60 days" to "5°C for 60 days." The resulting product was used to determine epoxy equivalent (g / eq), XRD measurement, calculation of 150°C melt viscosity (Poise), the content (%) of epoxy resins (1-1) and (2-1), and measurement of melting point (°C). The resulting product was not crystalline, but rather an amorphous substance (viscous liquid) with a low softening point, and therefore was not subjected to pulverization.

[0305] Table 1 shows the results.

[0306] [Table 1]

[0307] Table 1

[0308]

[0309] [Evaluation of results]

[0310] According to Examples 1 to 4, the polycrystals of bisphenol diglycidyl ether of the present embodiment crystallize in a short time, thereby shortening the process time. Furthermore, no sticking occurs in the apparatus during pulverization, thereby reducing the cleaning load when sticking occurs.

[0311] Furthermore, the polycrystals of bisphenol diglycidyl ether of this embodiment have low melt viscosity and are excellent in kneading properties and inorganic filler filling properties during encapsulation material production, thereby providing a highly fluid semiconductor encapsulation material that prevents wire displacement during semiconductor production.

[0312] Based on these results, the polycrystals of bisphenol-type diglycidyl ether according to this embodiment have excellent crushing properties and fluidity, and thus can improve productivity in the production of epoxy resins, semiconductor packaging materials, etc. Furthermore, the polycrystals of bisphenol-type diglycidyl ether according to this embodiment can improve production efficiency in the production of the polycrystals themselves, reducing workload.

Claims

1. A polycrystalline bisphenol diglycidyl ether comprising an epoxy compound represented by the following formula (1), wherein in a powder X-ray diffraction pattern measured using CuKα radiation, the crystallite size calculated from a peak having a diffraction angle 2θ at 8.9 to 9.3 degrees is In the formula (1), R 1 ~R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, or an alkynyl group having 2 to 12 carbon atoms which may have a substituent.

2. The polycrystalline form of bisphenol diglycidyl ether according to claim 1, wherein The average particle size is 0.5 to 10,000 μm. The polycrystalline material of bisphenol diglycidyl ether according to claim 1 or 2, which is a pulverized product.

4. The polycrystalline form of bisphenol diglycidyl ether according to claim 1 or 2, wherein The melting point is above 80°C.

5. The polycrystalline form of bisphenol diglycidyl ether according to claim 1 or 2, wherein The crystallite size calculated from the peak at a diffraction angle 2θ of 15.1 to 15.5 degrees in the powder X-ray diffraction pattern measured with CuKα radiation is 6. The polycrystalline form of bisphenol diglycidyl ether according to claim 1 or 2, wherein The powder X-ray diffraction pattern measured using CuKα radiation further has diffraction peaks at diffraction angles 2θ of 15.1 to 15.5 degrees, 19.4 to 19.8 degrees, and 24.9 to 25.3 degrees.

7. The polycrystalline form of bisphenol diglycidyl ether according to claim 1 or 2, wherein further comprising an epoxy compound represented by the following formula (2), In the formula (2), R 11 ~R 18 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, or an alkynyl group having 2 to 12 carbon atoms which may have a substituent; R 19 ~R 21 Each of them is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent, wherein R 19 With the R 20 They may bond to each other to form a ring structure having 1 to 12 carbon atoms.

8. A resin composition comprising the polycrystal of bisphenol diglycidyl ether according to claim 1 or 2 and a curing agent, wherein the curing agent is contained in an amount of 0.01 to 1000 parts by mass based on 100 parts by mass of all epoxy resin components as solid content.

9. The resin composition according to claim 8, wherein The curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent.

10. A cured product of the resin composition according to claim 8. 11 . An electric or electronic component comprising a resin composition containing a polycrystal of the bisphenol-type diglycidyl ether according to claim 1 . 12 . An electric or electronic component comprising a cured product of a resin composition containing a polycrystal of the bisphenol diglycidyl ether according to claim 1 .

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