Polyhydroxy resin, epoxy resin, method for producing the same, epoxy resin composition using the same, and cured product

Abstract

The present invention provides a polyhydroxy resin and an epoxy resin thereof which are useful in applications such as lamination, molding, casting, and bonding, and which can produce a cured product having excellent heat resistance, low thermal expansion, and moisture resistance. The present invention relates to a polyhydroxy resin represented by the following general formula (1) (wherein A represents a divalent aromatic group and n represents a number from 1 to 10). The present invention relates to an epoxy resin obtained by reacting the polyhydroxy resin with epichlorohydrin.

Description

Technical Field

[0001] The present invention relates to epoxy resins, intermediates and curing agents thereof, epoxy resin compositions using the same and cured products thereof, which provide cured products having excellent flame retardancy, moisture resistance, heat resistance and adhesion to metal substrates, and are suitable for use as insulating materials in the electrical and electronic fields such as printed wiring boards and semiconductor sealing. Background Art

[0002] In recent years, especially with the progress in the field of cutting-edge materials, the development of higher-performance base resins is required. For example, in the field of semiconductor sealing, the problem of package cracking has become increasingly serious due to the thinning and large-area packaging of high-density packaging in recent years and the popularization of surface mounting methods. As base resins, there is a strong demand for improved moisture resistance, heat resistance, and adhesion to metal substrates. In addition, recently, from the perspective of reducing environmental load, there is a trend to exclude halogen flame retardants, requiring base resins with better flame retardancy.

[0003] However, no epoxy resin that meets these requirements is known in the past. For example, the known bisphenol type epoxy resin is liquid at room temperature. Because it is easy to mix with curing agents, additives, etc. due to its excellent workability, it is widely used, but has problems in heat resistance and moisture resistance. In addition, as an epoxy resin to improve heat resistance, phenol novolac type epoxy resin is known, but has problems in moisture resistance and impact resistance. In addition, in Patent Document 1, for the purpose of improving moisture resistance and impact resistance, an epoxy compound of phenolic aralkyl resin is proposed, but it is insufficient in heat resistance and flame retardancy.

[0004] As a method for improving flame retardancy without using a halogen flame retardant, Patent Documents 2 and 3 disclose methods of adding a phosphate-based flame retardant. However, the method using a phosphate-based flame retardant has insufficient moisture resistance. In addition, there is a problem that the phosphate ester is hydrolyzed in a high temperature and high humidity environment, thereby reducing the reliability as an insulating material.

[0005] As an epoxy resin that does not contain phosphorus atoms or halogen atoms and has improved flame retardancy, Patent Document 4 proposes an example of using an aralkyl epoxy resin having a biphenyl structure as a semiconductor sealing material, but the flame retardancy is insufficient and the heat resistance is still insufficient.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 63-238122

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 9-235449

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 10-182792

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 11-140166 Summary of the invention

[0012] Therefore, an object of the present invention is to provide a polyhydroxy resin and an epoxy resin thereof, which can give a cured product having excellent heat resistance, low thermal expansion, moisture resistance, etc. and are useful in applications such as lamination, molding, casting, bonding, and the like, as well as a method for producing them and an epoxy resin composition using them and a cured product thereof.

[0013] That is, the present invention is a novel polyhydroxy resin represented by the following general formula (1).

[0014]

[0015] Here, A independently represents a divalent aromatic group. In addition, n represents a number of 1-10.

[0016] The present invention is also a method for producing a polyhydroxy resin of the general formula (1) by reacting 1 mol of an aromatic dihydroxy compound with 0.1 to 0.9 mol of a benzonitrile compound represented by the following general formula (2).

[0017]

[0018] wherein X independently represents a halogen atom.

[0019] Furthermore, the present invention is a novel epoxy resin represented by the following general formula (3).

[0020]

[0021] Here, A independently represents a divalent aromatic group. In addition, n represents a number of 1-10, and m represents a number of 1-15.

[0022] Furthermore, the present invention is a method for producing the novel epoxy resin represented by the general formula (3), characterized in that the polyhydroxy resin represented by the general formula (1) is reacted with epichlorohydrin.

[0023] Furthermore, the present invention provides an epoxy resin composition containing at least one of the above-mentioned epoxy resin or polyhydroxy resin as an essential component of the epoxy resin component or the curing agent component, and a cured product obtained by curing the epoxy resin composition.

[0024] The cured product obtained by curing the epoxy resin composition obtained from the epoxy resin or polyhydroxy resin of the present invention has excellent properties of heat resistance, low thermal expansion and moisture resistance, and can be used for lamination, molding, casting, bonding and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the GPC chart of polyhydroxy resin A.

[0026] Figure 2 This is the GPC chart of polyhydroxy resin B.

[0027] Figure 3 is the IR spectrum of polyhydroxy resin B.

[0028] Figure 4 This is the GPC chart of polyhydroxy resin D.

[0029] Figure 5 This is the GPC chart of polyhydroxy resin E.

[0030] Figure 6 This is the GPC chart of polyhydroxy resin F.

[0031] Figure 7 This is the GPC chart of polyhydroxy resin G.

[0032] Figure 8 This is the GPC chart of epoxy resin B.

[0033] Fig. 9 is the IR spectrum of epoxy resin B. DETAILED DESCRIPTION

[0034] Hereinafter, the present invention will be described in detail.

[0035] The polyhydroxy resin of the present invention is represented by the general formula (1).

[0036]

[0037] Here, A independently represents a divalent aromatic group. Examples of the divalent aromatic group include a benzene ring, a naphthalene ring, or a biphenylene group represented by the following formula (4).

[0038]

[0039] In formula (4), Y represents a direct bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, -COO-, -CONH-, -CH2-, -C(CH3)2-, -φ-, or 9,9-fluorenyl. Here, φ represents a phenylene group. In addition, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group, or a halogen atom.

[0040] A is preferably an unsubstituted or methyl-substituted benzene ring, a naphthalene ring or a biphenyl ring.

[0041] n represents the average number of repetitions, and is 1-10, preferably 1-5.

[0042] The hydroxyl equivalent of the polyhydroxy resin of the present invention is preferably 130 to 1000 g / eq., more preferably 150 to 600 g / eq. The melting point (or softening point) is preferably 40 to 250°C, more preferably 60 to 200°C.

[0043] Such a polyhydroxy resin is obtained by reacting an aromatic dihydroxy compound with a benzonitrile compound represented by the general formula (2).

[0044] Here, examples of the aromatic dihydroxy compound include divalent dihydroxybenzenes and dihydroxynaphthalenes substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, or a bisphenol compound represented by the following formula (5).

[0045]

[0046] In formula (5), Y, R1, and R2 have the same meanings as in formula (4).

[0047] Specific examples thereof include hydroquinone, 2,5-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, resorcinol, catechol, 1,5-naphthalene diol, 1,6-naphthalene diol, 1,7-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, and bisphenol fluorene.

[0048] Regarding the substitution position of dihydroxyl groups, as dihydroxybenzenes, 1,4-dihydroxy or 1,3-dihydroxy groups are preferred, as dihydroxynaphthalenes, 1,5-dihydroxy, 1,6-dihydroxy, 2,6-dihydroxy or 2,7-dihydroxy groups are preferred, and as bisphenol compounds, 4,4'-dihydroxy groups are preferred. In the aromatic dihydroxy compounds used, these dihydroxyl substitution groups preferably account for 50 mol% or more.

[0049] Among these aromatic dihydroxy compounds, dihydroxybenzenes, dihydroxynaphthalenes and dihydroxybiphenyls are preferred from the viewpoints of heat resistance, moisture resistance and flame retardancy. The above aromatic dihydroxy compounds may be used alone or in combination of two or more.

[0050] In the benzonitrile compound of the general formula (2),

[0051]

[0052] X is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but preferably a fluorine atom or a chlorine atom. In addition, as the substitution position of the halogen atom, the 2,6-position is preferred. Specifically, 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, and 2,6-dibromobenzonitrile can be cited. Even when a halogen substituent other than the 2,6-position is used in combination, it is preferred that the 2,6-position halogen substituent in the benzonitrile compound is 50 mol% or more.

[0053] In the reaction of an aromatic dihydroxy compound and a benzonitrile compound, an excess amount of a bisphenol compound is used relative to the benzonitrile compound. The amount of the benzonitrile compound used is in the range of 0.1 to 0.9 moles, preferably in the range of 0.1 to 0.6 moles, relative to 1 mole of the aromatic dihydroxy compound. If it is greater than this value, the softening point of the resin becomes higher, hindering the molding workability. In addition, if it is less than this value, the amount of the aromatic dihydroxy compound used in excess increases after the reaction is completed. The remaining excess aromatic dihydroxy compound does not need to be removed and can be directly used as a raw material or curing agent for epoxy resin, but since the content of the resin of general formula (1) or (3) is reduced, the effect of improving properties such as heat resistance, moisture resistance and flame retardancy is reduced.

[0054] The reaction is usually carried out in the presence of a basic catalyst, which can be selected from tertiary amine compounds, quaternary ammonium compounds, imidazole compounds, tertiary phosphine compounds, quaternary A compound, and a compound of at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, and an alkali metal hydrogen carbonate.

[0055] Examples of the tertiary amine compound include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, tri-n-hexylamine, dimethylbenzylamine, diethylbenzylamine, tribenzylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0056] Examples of the quaternary ammonium compound include quaternary ammonium hydroxide compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and triethylbenzylammonium hydroxide; quaternary ammonium chloride compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, trimethylbenzylammonium chloride, and triethylbenzylammonium chloride; quaternary ammonium bromide compounds such as tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-propylammonium bromide, tetra-n-butylammonium bromide, trimethylbenzylammonium bromide, and triethylbenzylammonium bromide; and quaternary ammonium iodide compounds such as tetramethylammonium iodide, tetraethylammonium iodide, tetra-n-propylammonium iodide, tetra-n-butylammonium iodide, trimethylbenzylammonium iodide, and triethylbenzylammonium iodide.

[0057] Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2',4',6'-trimethylbenzoyl)-2-ethylimidazole, 1-(2',6'-dichlorobenzoyl)-2-methylimidazole, 1-(2',4',6'-trimethylbenzoyl)-2-methylimidazole, and 1-(2',4',6'-trimethylbenzoyl)-2-phenylimidazole.

[0058] Examples of the tertiary phosphine compound include triethylphosphine, tri-n-butylphosphine, triphenylphosphine, and trinonylphenylphosphine. Compounds such as tetramethyl hydroxide Quaternary Hydroxide Compound; Tetramethyl Chloride Tetrabutyl chloride Tetraphenyl chloride Tetrabutyl bromide Methyltriphenylphosphine bromide n-Butyltriphenylphosphine bromide Methyltriphenylphosphine bromide Ethyltriphenylphosphine bromide Halogenation Season Compound; Ethyltriphenylacetic acid EtOAc Compounds, etc.

[0059] Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.

[0060] Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, and the like. Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.

[0061] These basic catalysts can be added to the reaction system alone or dissolved in water or a solvent. The basic catalyst is usually used in an amount of 0.001 to 10 mol %, preferably 0.05 to 5 mol %, per 1 mol of phenolic hydroxyl groups in the aromatic dihydroxy compound.

[0062] Usually, the reaction is carried out at 10 to 250° C. for 1 to 20 hours. As the reaction solvent, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, benzene, toluene, chlorobenzene, dichlorobenzene, etc. can be used.

[0063] After the reaction is completed, the catalyst is removed by neutralization, water washing or the like, and the remaining solvent is removed from the system by water washing, vacuum distillation or the like as needed to obtain a hydroxy resin. The unreacted aromatic dihydroxy compound may be removed from the system by water washing, vacuum distillation or the like, or may not be removed.

[0064] The epoxy resin represented by the general formula (3) of the present invention,

[0065]

[0066] It is obtained by reacting the polyhydroxy resin represented by the above general formula (1) with epichlorohydrin.

[0067] In the formula (3), A and n have the same meanings as in the formula (1) representing the polyhydroxy resin as a raw material. m represents a number of 1 to 15, and the average value is preferably 1.1 to 6.

[0068] The epoxy equivalent of the epoxy resin of the present invention is preferably 180 to 1200 g / eq., more preferably 200 to 650 g / eq. The melting point (or softening point) is preferably 40 to 250° C., more preferably 60 to 200° C. The melt viscosity at 150° C. is preferably 0.1 to 10 Pa·s, more preferably 0.1 to 5 Pa·s.

[0069] This reaction can be carried out in the same manner as a conventional epoxidation reaction. For example, there can be mentioned a method in which the polyhydroxy resin represented by the general formula (1) is dissolved in an excess of epichlorohydrin, and then reacted at 50 to 150°C, preferably 60 to 120°C, for 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. In this case, the amount of the alkali metal hydroxide used is 0.8 to 2 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of the hydroxyl groups in the polyhydroxy resin. In addition, epichlorohydrin is used in excess relative to the hydroxyl groups in the polyhydroxy resin, usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, relative to 1 mol of the hydroxyl groups in the polyhydroxy resin. In addition, a quaternary ammonium salt or the like may be added during the reaction. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the like, and the amount thereof added is preferably in the range of 0.1 to 2.0 wt% relative to the polyhydroxy resin. If the amount is less than this, the effect of adding the quaternary ammonium salt is small. If it is more than this, the generation of poorly hydrolyzable chlorine increases, and high purification becomes difficult. In addition, polar solvents such as dimethyl sulfoxide and diethylene glycol dimethyl ether can be used, and the amount added is preferably in the range of 10 to 200 wt% relative to the polyhydroxy resin. If it is less than this, the effect of addition is small. If it is more than this, the volumetric efficiency decreases, which is not economically preferred. After the reaction is completed, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone. After filtering, the inorganic salt is removed by washing with water, and then the solvent is distilled off, thereby obtaining the target epoxy resin. The epoxy resin is mainly composed of a substance represented by the general formula (3), but may contain a glycidyl ether of a compound obtained by adding one or more naphthyl methane groups to the aromatic ring of the novel polyhydroxy resin of the general formula (1). In addition, it may contain a substance in which the epoxy group oligomer in the epoxy resin of the present invention is converted into an ether bond.

[0070] The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent, and contains at least one of the epoxy resin represented by the general formula (3) as an epoxy resin component and the polyhydroxy resin represented by the general formula (1) as a curing agent component as an essential component.

[0071] When the epoxy resin represented by the general formula (3) is an essential component, all substances generally known as curing agents for epoxy resins can be used. For example, there are dicyandiamide, polyphenols, acid anhydrides, aromatic and aliphatic amines, etc. Specifically, as polyphenols, for example, there are divalent phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol, or trivalent or higher phenols represented by tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthol novolac, and polyethylene phenol, as well as phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol, or trivalent or higher phenols represented by tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthol novolac, and polyethylene phenol, and phenols, naphthols, or bisphenol A, bisphenol S, bisphenol S, bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol. Polyphenolic compounds synthesized from divalent phenols such as phenol F, bisphenol S, bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol by condensation agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylene glycol; and acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, and trimellitic anhydride. In addition, as amines, there are aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or a polyhydroxy resin represented by the general formula (1). The resin composition of the present invention can use one of these curing agents or a mixture of two or more thereof.

[0072] In this case, the blending amount of the epoxy resin of the present invention is preferably in the range of 5 to 100 wt %, more preferably in the range of 50 to 100 wt % based on the total amount of the epoxy resin.

[0073] As the epoxy resin when the polyhydroxy resin represented by the general formula (1) is an essential component of the curing agent component, all common epoxy resins having two or more epoxy groups in the molecule can be used. For example, there are bisphenol A, bisphenol S, bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol and other divalent phenols or tri-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac and other trivalent or higher phenols, or glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A or the above-mentioned polyfunctional epoxy resin represented by the general formula (1). These epoxy resins can be used alone or in combination of two or more.

[0074] In this case, the amount of the polyhydroxy resin of the present invention blended is preferably in the range of 5 to 100 wt %, more preferably in the range of 50 to 100 wt %, based on the entire epoxy resin.

[0075] In addition, in the epoxy resin composition of the present invention, which is an essential component of the epoxy resin represented by the general formula (3) or the polyhydroxy resin represented by the general formula (1), or both, oligomers or polymer compounds such as polyesters, polyamides, polyimides, polyethers, polyurethanes, petroleum resins, indene-coumarone resins, and phenoxy resins can be appropriately combined, and additives such as inorganic fillers, pigments, flame retardants, thixotropy imparting agents, coupling agents, and fluidity improvers can also be combined. As inorganic fillers, for example, spherical or crushed fused silica, crystalline silica and other silica powders, alumina powders, glass powders or mica, talc, calcium carbonate, alumina, hydrated alumina, etc. can be cited. As pigments, there are organic or inorganic body pigments, flaky pigments, etc. As thixotropy imparting agents, silicon systems, castor oil systems, aliphatic amide waxes, oxidized polyethylene waxes, organic bentonite systems, etc. can be cited. Further, as needed, a curing accelerator that has always been known can be used. For example, there are amines, imidazoles, organic phosphines, Lewis acids, etc. As the addition amount, it is usually in the range of 0.2 to 5 parts by weight relative to 100 parts by weight of the epoxy resin. In addition, as necessary, the resin composition of the present invention can use release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, flame retardants such as antimony trioxide, stress reducing agents such as silicone oil, lubricants such as calcium stearate, etc.

[0076] The cured product of the present invention can be obtained by molding the epoxy resin composition described above by casting, compression molding, transfer molding, etc. The temperature during molding is usually in the range of 120 to 220°C.

[0077] Example

[0078] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.

[0079] Example 1 (Manufacture of polyhydroxy resin A)

[0080] In a 2L 4-necked separable flask, 128.1g of hydroquinone was dissolved in 700g of N-methylpyrrolidone (NMP), and then 139.3g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Thereafter, 50.0g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 150°C for reaction for 6 hours. After 121.1g of acetic acid was added to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of methyl isobutyl ketone (MIBK) was added to the reaction solution, and after the product was dissolved, the generated salt and unreacted hydroquinone were removed by washing with water. Thereafter, MIBK was removed by distillation under reduced pressure to obtain 71g of polyhydroxy resin (polyhydroxy resin A) in the form of a yellow powder. The hydroxyl equivalent of the obtained hydroxy resin A is 162g / eq., and the melting point is 255°C. The GPC graph is shown in Figure 1 .

[0081] The melt viscosity was measured using CAP2000H manufactured by Brookfield, and the GPC measurement was performed using the following apparatus: HLC-8320 (manufactured by Tosoh Corporation) and columns: TSKgel SuperHZ2500×2 and TSKgel SuperHZ2000×2 (both manufactured by Tosoh Corporation), under the conditions of solvent: tetrahydrofuran, flow rate: 0.35 ml / min, temperature: 40°C, and detector: RI.

[0082] Example 2 (Manufacture of polyhydroxy resin B)

[0083] In a 2L 4-necked separable flask, 80.0g of hydroquinone was dissolved in 700g of N-methylpyrrolidone (NMP), and then 119.4g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Thereafter, 50.0g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 150°C for reaction for 6 hours. After 103.8g of acetic acid was added to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of methyl isobutyl ketone (MIBK) was added to the reaction solution, the product was dissolved, and the generated salt was removed by washing with water. Thereafter, MIBK was removed by distillation under reduced pressure to obtain 74g of yellow powdery hydroxy resin (polyhydroxy resin B). The hydroxyl equivalent of the obtained polyhydroxy resin B is 220g / eq., and the melting point is 216°C. The GPC graph is shown in Figure 2 , the infrared absorption spectrum is shown in Figure 3 .

[0084] Example 3 (Manufacture of polyhydroxy resin C)

[0085] In a 2L 4-necked separable flask, 128g of resorcinol was dissolved in 700g of NMP, and then 139.3g of potassium carbonate was added. The mixture was heated to 120°C while stirring under a nitrogen stream. Subsequently, 50g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 150°C for reaction for 6 hours. After 121.1g of acetic acid was added to the reaction solution for neutralization, NMP was distilled off under reduced pressure. 500mL of MIBK was added to the reaction solution, and after the product was dissolved, the generated salt and unreacted resorcinol were removed by washing with water. Subsequently, MIBK was removed by vacuum distillation to obtain 80g of polyhydroxy resin (polyhydroxy resin C) in the form of a yellow powder. The hydroxyl equivalent of the obtained hydroxy resin C was 164g / eq., and the melting point was 146°C.

[0086] Example 4 (Manufacture of polyhydroxy resin D)

[0087] In a 2L 4-necked separable flask, 99.5g of 2,7-dihydroxynaphthalene was dissolved in 700g of NMP, and then 85g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Subsequently, 35.6g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 150°C for reaction for 6 hours. After 73.9g of acetic acid was added to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of MIBK was added to the reaction solution, the product was dissolved, and the generated salt was removed by washing with water. Subsequently, MIBK was removed by distillation under reduced pressure to obtain 123g of polyhydroxy resin (polyhydroxy resin D). The hydroxyl equivalent of the obtained hydroxy resin D is 204g / eq., and the melting point is 133°C. The GPC graph is shown in Figure 4 .

[0088] Example 5 (Manufacturing of polyhydroxy resin E)

[0089] In a 1L 4-necked separable flask, 73.5g of 1,5-dihydroxynaphthalene was dissolved in 250g of NMP, and then 21.6g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Subsequently, 26.1g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 150°C for reaction for 5 hours. After adding 21.6g of acetic acid to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of MIBK was added to the reaction solution, and after dissolving the product, the generated salt was removed by washing with water. Subsequently, MIBK was removed by distillation under reduced pressure to obtain 71g of polyhydroxy resin (polyhydroxy resin E). The hydroxyl equivalent of the obtained hydroxy resin E is 180g / eq., and the melting point is 192°C. The GPC graph is shown in Figure 5 .

[0090] Example 6 (Manufacture of polyhydroxy resin F)

[0091] In a 1L 4-necked separable flask, 112.9g of 4,4'-dihydroxybiphenyl was dissolved in 500g of NMP, and then 49.8g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Subsequently, 52.1g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 145°C for reaction for 6 hours. After 43.2g of acetic acid was added to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of MIBK was added to the reaction solution, the product was dissolved, and the generated salt was removed by washing with water. Subsequently, MIBK was removed by distillation under reduced pressure to obtain 128g of polyhydroxy resin (polyhydroxy resin F). The hydroxyl equivalent of the obtained hydroxy resin F is 270g / eq., and the melting point is 337°C. The GPC graph is shown in Figure 6 .

[0092] Example 7 (Manufacture of polyhydroxy resin G)

[0093] In a 1L 4-necked separable flask, 38.2g of 4,4'-dihydroxydiphenyl ether was dissolved in 500g of NMP, and then 23.9g of potassium carbonate was added. Under a nitrogen flow, the temperature was raised to 120°C while stirring. Subsequently, 25.0g of 2,6-dichlorobenzonitrile was added, and the temperature was raised to 145°C for reaction for 6 hours. After adding 20.8g of acetic acid to the reaction solution for neutralization, the NMP was distilled off under reduced pressure. 500mL of MIBK was added to the reaction solution, the product was dissolved, and the generated salt was removed by washing with water. Subsequently, MIBK was removed by distillation under reduced pressure to obtain 50g of polyhydroxy resin (polyhydroxy resin G). The hydroxyl equivalent of the obtained hydroxy resin G is 630g / eq., and the melting point is 225°C. The GPC graph is shown in Figure 7 .

[0094] Example 8 (Manufacture of epoxy resin A)

[0095] 15 g of the polyhydroxy resin A obtained in Example 1 was dissolved in 130 g of epichlorohydrin and 33 g of diethylene glycol dimethyl ether, and 7.8 g of a 48% sodium hydroxide aqueous solution was added dropwise at 60°C for 4 hours under reduced pressure (about 100 mmHg). During this period, the generated water was removed to the outside of the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition was completed, the reaction was continued for another hour. Thereafter, epichlorohydrin and diethylene glycol dimethyl ether were distilled off under reduced pressure, dissolved in 120 mL of methyl isobutyl ketone, and the salt generated was removed by filtration. Thereafter, 0.4 g of a 48% sodium hydroxide aqueous solution was added and reacted at 80°C for 2 hours. After the reaction, the mixture was filtered, washed with water, and the methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 16 g of a yellow powdery epoxy resin (epoxy resin A). The obtained epoxy resin A had a melting point of 147.3°C and an epoxy equivalent of 230 g / eq. Here, hydrolyzable chlorine was prepared by dissolving 0.5 g of a resin sample in 1,4-dichlorobenzene. After adding 30 ml of oxane, the mixture was boiled and refluxed in 5 ml of 1N-KOH / methanol solution for 30 minutes, and potentiometric titration was performed with a silver nitrate solution to determine the content.

[0096] Example 9 (Manufacture of epoxy resin B)

[0097] 22 g of the polyhydroxy resin B obtained in Example 2 was dissolved in 142 g of epichlorohydrin and 36 g of diethylene glycol dimethyl ether, and 8.1 g of a 48% aqueous sodium hydroxide solution was used to react in the same manner as in Example 8 to obtain 26 g of an epoxy resin (epoxy resin B) that was viscous at room temperature. The epoxy equivalent of the epoxy resin B obtained was 290 g / eq., and the melt viscosity at 150°C was 0.54 Pa·s. The GPC chart is shown in FIG. Figure 8 , the infrared absorption spectrum is shown in Fig. 9 .

[0098] Example 10 (Production of Epoxy Resin C)

[0099] 30 g of the polyhydroxy resin C obtained in Example 3 was dissolved in 260 g of epichlorohydrin and 65 g of diethylene glycol dimethyl ether, and 15.6 g of a 48% aqueous sodium hydroxide solution was used to react in the same manner as in Example 8 to obtain 36 g of an epoxy resin (epoxy resin C) that was viscous at room temperature. The epoxy equivalent of the obtained epoxy resin C was 242 g / eq., and the melt viscosity at 150° C. was 0.22 Pa·s.

[0100] Example 11 (Production of Epoxy Resin D)

[0101] 50 g of the polyhydroxy resin D obtained in Example 4 was dissolved in 340 g of epichlorohydrin and 85 g of diethylene glycol dimethyl ether, and 19.6 g of a 48% aqueous sodium hydroxide solution was used to react in the same manner as in Example 8 to obtain 56 g of an epoxy resin (epoxy resin D) which was solid at room temperature. The epoxy equivalent of the obtained epoxy resin D was 227 g / eq., and the melt viscosity at 150° C. was 0.61 Pa·s.

[0102] Example 12 (Production of Epoxy Resin E)

[0103] 45 g of the polyhydroxy resin E obtained in Example 5 was dissolved in 400 g of epichlorohydrin and 60 g of diethylene glycol dimethyl ether, and 24.2 g of a 48% aqueous sodium hydroxide solution was used to react in the same manner as in Example 8 to obtain 38 g of an epoxy resin (epoxy resin E) which was solid at room temperature. The epoxy equivalent of the obtained epoxy resin E was 224 g / eq., and the melt viscosity at 150° C. was 0.19 Pa·s.

[0104] Example 13 (Production of Epoxy Resin F)

[0105] 50 g of the polyhydroxy resin F obtained in Example 6 was dissolved in 260 g of epichlorohydrin and 65 g of diethylene glycol dimethyl ether, and 15.2 g of a 48% aqueous sodium hydroxide solution was used to react in the same manner as in Example 8 to obtain 35 g of an epoxy resin (epoxy resin F) which was solid at room temperature. The epoxy equivalent of the obtained epoxy resin F was 317 g / eq. and the melting point was 179.5°C.

[0106] Examples 14 to 20 and Comparative Example 1

[0107] Using the polyhydroxy resin or epoxy resin synthesized in Examples 1 to 13, o-cresol novolac type epoxy resin (epoxy equivalent 197, softening point 54°C, melt viscosity at 150°C 90 mPa·s; EOCN-1020, manufactured by Nippon Kayaku; epoxy resin H), phenol novolac (OH equivalent 104, softening point 83°C, melt viscosity at 150°C 0.3 Pa·s; BRG-557, manufactured by AICA Industries, Ltd.; hydroxy resin H), and triphenylphosphine as a curing accelerator, a resin composition is prepared according to the formulation shown in Table 1.

[0108] The resin composition was used for molding (150°C, 5 minutes) and then post-cured (175°C, 4 hours) to obtain test pieces, which were used for various physical property tests. The test methods are as follows. The glass transition temperature and thermal expansion coefficient were determined using a TMA7100 thermomechanical measuring apparatus manufactured by Hitachi High-Tech Science Corporation at a heating rate of 10°C / minute. The thermal decomposition temperature and residual carbon rate were determined using a TG / DTA7300 thermogravimetric measuring apparatus manufactured by Hitachi High-Tech Science Corporation under a nitrogen gas flow and a heating rate of 10°C / minute to determine the thermal decomposition temperature at a weight reduction of 5 wt% and the residual carbon rate at 700°C. The water absorption rate was calculated using a test piece with a diameter of 50 mm and a thickness of 3 mm, based on the weight change rate when the test piece was hydrated at 85°C and 85%RH for 100 hours after post-curing.

[0109] The results are shown in Table 1.

[0110]

[0111] Industrial Applicability

[0112] The polyhydroxy resin and epoxy resin of the present invention, as well as the production method thereof, the epoxy resin composition using the same and the cured product thereof are excellent in heat resistance, low thermal expansion, moisture resistance, etc., and are suitable for use as insulating materials in the electrical and electronic fields such as printed wiring boards and semiconductor sealing.

Claims

1. An epoxy resin, characterized in that It is represented by the following general formula (3): Here, A is independently an unsubstituted or methyl-substituted benzene ring, naphthalene ring or biphenyl ring; n is a number of 1-10; and m is a number of 1-15.

2. A method for producing an epoxy resin according to claim 1, characterized in that: reacting a polyhydroxy resin with epichlorohydrin, The polyhydroxy resin is represented by the following general formula (1), and the polyhydroxy resin is a mixture. Here, A is independently an unsubstituted or methyl-substituted benzene ring, naphthalene ring or biphenyl ring, and n is an average repeating number, which represents a number of 1 to 10.

3. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 1 is added as an essential component.

4. A cured product obtained by curing the epoxy resin composition according to claim 3.

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