KR101752222B1

KR101752222B1 - Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product

Info

Publication number: KR101752222B1
Application number: KR1020127017889A
Authority: KR
Inventors: 마사시 카지; 코이치로 오가미
Original assignee: 신닛테츠 수미킨 가가쿠 가부시키가이샤
Priority date: 2009-12-14
Filing date: 2010-12-13
Publication date: 2017-06-29
Also published as: TWI494338B; SG181697A1; TW201144347A; WO2011074517A1; KR20120115301A; JPWO2011074517A1; CN102656204B; CN102656204A; JP5166610B2; MY156527A

Abstract

An epoxy resin which is excellent in handleability as a low viscosity and a solid and has excellent heat resistance, moisture resistance and thermal conductivity and is useful for applications such as lamination, molding, casting, and bonding, and epoxy resin compositions and cured products using the same .
The epoxy resin of the present invention is an epoxy resin represented by the following general formula (1) and having crystallinity with an endothermic peak temperature based on the melting point in differential scanning calorimetry in the range of 100 to 150 캜. The epoxy resin composition of the present invention is an epoxy resin composition containing the epoxy resin and a curing agent as essential components. In the general formula (1), n represents an average value of 0.2 to 4.0, and G represents a glycidyl group.

Description

EPOXY RESIN, PROCESS FOR PRODUCTION THEREOF, EPOXY RESIN COMPOSITION USING SAME, AND CURED PRODUCT <br> <br> <br> Patents - stay tuned to the technology EPOXY RESIN,

The present invention relates to a crystalline epoxy resin, a process for producing the same, an epoxy resin composition using the same, and a cured product.

In recent years, development of a higher-performance base resin has been required, particularly with advances in the advanced materials field. For example, in the field of semiconductor encapsulation, a base resin having high heat resistance and excellent thermal decomposition stability is required due to the progress of semiconductor for vehicle use. On the other hand, since high-density mounting is also advanced, the high filler ratio of the inorganic filler is directed, and the base resin is also required to have a low viscosity. In addition, improvement of high-temperature reliability for coping with a severe use environment is required, and improvement of thermal conductivity is also demanded from the viewpoint of improving heat dissipation.

However, it has not yet been found that satisfying these demands is known for epoxy resins known from the prior art. For example, Patent Document 1 proposes a naphthol aralkyl type epoxy resin which is excellent in heat resistance and moisture resistance. However, it is not sufficient in terms of heat resistance and has a high viscosity, so that it is not suitable for increasing the charging rate of an inorganic filler. In addition, Patent Document 2 discloses an aralkyl type epoxy resin in which 4,4'-dihydroxybiphenyl is linked with a p-xylylene group. However, it has a problem in moisture resistance and flame retardancy. Patent Document 3 discloses a biphenyl aralkyl type epoxy resin having a structure in which a bisphenol compound is linked with a biphenylene group. However, since it is a dendritic resin having no crystallinity, the viscosity and the softening point are increased, resulting in problems in moldability.

Japanese Patent Application Laid-Open No. 1-252624 Japanese Patent Application Laid-Open No. 4-255714 Japanese Patent Application Laid-Open No. 8-239454

Accordingly, an object of the present invention is to provide an epoxy resin which is excellent in handleability as a low viscosity and a solid, has excellent heat resistance, moisture resistance and thermal conductivity and is useful for applications such as lamination, molding, casting, And an epoxy resin composition and a cured product thereof.

That is, the present invention relates to an epoxy resin represented by the following general formula (1) and having crystallinity with an endothermic peak temperature based on the melting point in differential scanning calorimetry in the range of 100 to 150 ° C.

(Wherein n represents an average value of 0.2 to 4.0, and G represents a glycidyl group.)

Also, the present invention relates to a process for producing a biphenyl-based condensation product by reacting 0.1 to 0.4 mol of a biphenyl-based condensing agent represented by the following general formula (2) with respect to 1 mol of 4,4'-dihydroxybiphenyl, Having an endothermic peak temperature based on the melting point in a differential scanning calorimetry analysis obtained by reacting a polyhydric hydroxy resin with epichlorohydrin in the range of 100 to 150 ° C .

(Wherein X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms).

(Where n represents an average value of 0.2 to 4.0).

The present invention also relates to an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition comprises the epoxy resin as an epoxy resin component, and a cured product obtained by curing the epoxy resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided an epoxy resin which is excellent in handleability as a low viscosity and a solid, has excellent heat resistance, moisture resistance and thermal conductivity and is useful for applications such as lamination, molding, A cured product can be provided.

1 is a GPC chart of the resin obtained in Reference Example 1. Fig.
2 is a GPC chart of the resin obtained in Example 1. Fig.
3 is a DSC chart of the resin obtained in Example 1. Fig.

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention is a mixture of components represented by the general formula (1) in which the value of the repeating unit (n) is different. Here, n represents an average value of 0.2 to 4.0. If it is smaller than this range, the crystallinity becomes strong and the melting point becomes high and the handling property decreases. If it is larger than the above range, the crystallinity decreases and the viscosity increases and the moldability decreases. From the viewpoints of low viscosity, handling and moldability, it is preferable that the content ratio of n = 0 is in the range of 30 to 60%. The average value of n in this specification refers to the number average value.

The epoxy resin of the present invention has crystallinity and crystallizes in a solid state. The temperature of the endothermic peak based on the melting point in the differential scanning calorimetry measured at a heating rate of 10 ° C / min is in the range of 100 to 150 ° C, preferably 120 to 150 ° C. If it is higher than the above range, the compatibility with the curing agent when adjusting the epoxy resin composition is lowered. If it is lower than this range, problems such as blocking of the epoxy resin composition are caused and the handling property is lowered. Depending on the crystalline state of the epoxy resin, a plurality of melting point peaks sometimes appear, and the endothermic peak temperature referred to here corresponds to the largest peak. The heat absorption amount of the peak is considered to indicate the degree of crystallinity, which is usually in the range of 20 to 80 J / g in terms of the resin component. If it is smaller than the above range, the degree of crystallinity is low and the handling property is deteriorated.

The epoxy resin of the present invention is obtained by reacting a polyhydric hydroxy resin represented by the general formula (3) with epichlorohydrin. In the invention of the epoxy resin, the production method is not limited thereto. However, by explaining the invention of the production method, understanding of the epoxy resin of the present invention is facilitated, and therefore, a method for producing a polyhydric hydroxy resin and an epoxy resin which are raw materials of the epoxy resin will be described.

The polyhydric hydroxy resin represented by the general formula (3) is a mixture of components having different values of n, and n is an average value of 0.2 to 4.0. If it is smaller than this range, the crystallinity becomes strong, and the solubility in epichlorohydrin in the synthesis of the epoxy resin decreases, and the melting point of the resulting epoxy resin increases and the handleability decreases. If it is larger than the above range, the crystallinity decreases and the viscosity increases and the moldability decreases. From the viewpoints of low viscosity, handling and moldability, it is preferable that the content ratio of n = 0 is in the range of 30 to 60%.

Such a polyhydric hydroxy resin is obtained by reacting 4,4'-dihydroxybiphenyl with a biphenyl-based condensing agent represented by the general formula (2).

In the general formula (2), X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms. Specific examples thereof include 4,4'-bis hydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl , And 4,4'-bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4'-bishydroxymethylbiphenyl and 4,4'-bischloromethylbiphenyl are preferable, and from the viewpoint of reducing ionic impurities, 4,4'-bishydroxy Methyl biphenyl and 4,4'-bismethoxymethyl biphenyl are preferable.

In the reaction, the molar ratio of the biphenyl-based condensing agent to the 1 mole of 4,4'-dihydroxybiphenyl should be 1 mole or less, and is generally in the range of 0.1 to 0.5 mole, 0.2 to 0.4 moles. If it is less than this range, the crystallinity becomes strong, and the solubility in epichlorohydrin decreases when synthesizing an epoxy resin, and the melting point of the obtained epoxy resin increases, and the handling property decreases. On the other hand, if it is larger than the above range, the crystallinity of the resin deteriorates, and the softening point and the melt viscosity increase, resulting in deterioration in handling workability and moldability.

When 4,4'-bischloromethylbiphenyl is used as the condensing agent, the reaction may be carried out in the absence of a catalyst. Usually, the condensation reaction is carried out in the presence of an acidic catalyst. As the acidic catalyst, it is possible to appropriately select from a well-known mineral acid and an organic acid, and examples thereof include a mineral acid such as hydrochloric acid, sulfuric acid and phosphoric acid, and a mineral acid such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, Organic acids such as trifluoromethanesulfonic acid, and Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids.

This reaction is carried out at 10 to 250 ° C for 1 to 20 hours. In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent. After completion of the reaction, the solvent or water and alcohols produced by the condensation reaction are removed, if necessary.

The polyhydric hydroxy resin thus obtained can be used as an epoxy resin curing agent in addition to being used as a raw material for an epoxy resin. Further, it can be applied as a phenol resin molding material by further combining with a curing agent such as hexamine.

A method for producing an epoxy resin of the present invention by reaction of a polyhydric hydroxy resin represented by the general formula (3) with epichlorohydrin will be described. This reaction can be carried out in the same manner as in the known epoxidation reaction.

For example, the polyhydric hydroxy resin represented by the general formula (3) is dissolved in excess epichlorohydrin and then reacted in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at a temperature of 50 to 150 ° C, And the reaction is carried out at 120 占 폚 for 1 to 10 hours. The amount of epichlorohydrin to be used is 0.8 to 2 moles, preferably 0.9 to 1.2 moles per mole of the hydroxyl group in the polyhydric hydroxy resin. After completion of the reaction, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off, The desired epoxy resin represented by the following formula (1) can be obtained. A catalyst such as a quaternary ammonium salt may be used when carrying out the epoxidation reaction.

The purity of the epoxy resin of the present invention, especially the amount of hydrolyzable chlorine, is preferably as small as possible from the viewpoint of improving the reliability of the applied electronic parts. Is not particularly limited, but is preferably 1000 ppm or less, more preferably 500 ppm or less. The hydrolyzable chlorine in the present invention means a value measured by the following method. That is, after 0.5 g of the sample was dissolved in 30 ml of dioxane, 1N-KOH and 10 ml were added and the mixture was refluxed for 30 minutes. After cooling to room temperature, 100 ml of 80% acetone water was added, ₃ aqueous solution by titration.

The epoxy resin composition of the present invention includes an epoxy resin and a curing agent, and the epoxy resin component includes the epoxy resin of the above general formula (1).

In the epoxy resin composition of the present invention, in addition to the epoxy resin of the general formula (1) used as an essential component, other common epoxy resins having two or more epoxy groups in the molecule may be used in combination. Examples thereof include bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl- Dihydroxybiphenyl, 2,2'-biphenol, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxy Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3 -Dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene , Allyl or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, and the like. Phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolac, p-cresol novolac, xylenol novolak, poly- p- hydroxystyrene, tris- (4-hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allyl pyrogallol, polyallylated pyrogallol, Tri- or higher-valent phenols such as 1,2,4-benzene triol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin and dicyclopentadiene resin, or tetrabromobisphenol And glycidyl ether compounds derived from halogenated bisphenols such as A and the like. These epoxy resins may be used alone or in combination of two or more.

The epoxy resin composition of the present invention preferably contains, as an epoxy resin, the epoxy resin of the above general formula (1) in an amount of 50 wt% or more of the epoxy resin component. More preferably, it is 70 wt% or more, and more preferably 80 wt% or more of the total epoxy resin. When the use ratio is less than this range, the moldability of the epoxy resin composition deteriorates, and the effect of improving the heat resistance, moisture resistance, thermal conductivity, and solder reflow resistance when formed into a cured product is small.

As the curing agent in the epoxy resin composition of the present invention, any curing agent generally known as an epoxy resin curing agent can be used. Examples thereof include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Polyhydric phenols are preferably used in the field of encapsulating electric / electronic parts requiring moisture resistance and heat resistance. These are specifically exemplified as follows. In the resin composition of the present invention, one or more of these curing agents may be used in combination.

Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin and naphthalenediol; (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolac, naphthol novolac, polyvinyl phenol and the like Representative trivalent or higher phenols and also phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol , And polyhydric phenolic compounds synthesized by condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol and the like. A polyhydric hydroxy resin represented by the general formula (3) can also be used.

Examples of the acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride, anhydrous nadic acid, and anhydrous trimellitic acid.

Examples of the amines include aromatic compounds such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p- And aliphatic amines such as amines, ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the resin composition of the present invention, one or more of these curing agents may be used in combination.

In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyesters, polyamides, polyimides, polyethers, polyphenylene ethers, polyurethanes, petroleum resins, indenecumarone resins and phenoxy resins may be appropriately mixed , An inorganic filler, a pigment, a flame retardant, a thixotropic agent, a coupling agent, and a flowability improver.

In the epoxy resin composition of the present invention, an inorganic filler can be blended. For example, silica powder such as fused silica or crystalline silica in a spherical or crushed form, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide , Powders of boron nitride, beryllium, zirconia, forsterite, stearate, spinel, mullite and titania, or beads obtained by spheroidizing these materials, potassium titanate, silicon carbide, silicon nitride, alumina And glass fibers may be used alone or in combination of two or more. Of the above inorganic fillers, alumina is preferable from the viewpoint of reducing the coefficient of linear expansion and from the viewpoint of high thermal conductivity. The filler shape is preferably 50% or more spherical in terms of fluidity at the time of molding and mold wear resistance, and spherical fused silica powder is particularly preferably used.

The addition amount of the inorganic filler is usually 50 wt% or more, preferably 70 wt% or more, and more preferably 80 wt% or more based on the epoxy resin composition. If it is less than this range, the desired effects of the present invention such as low hygroscopicity, low heat expansion, high heat resistance, and high thermal conductivity are not sufficiently exhibited. These effects are better as the addition amount of the inorganic filler is larger, but they do not improve according to the volume fraction thereof but remarkably improve from the specific addition amount. On the other hand, if the amount of the inorganic filler to be added is larger than the above range, the viscosity is increased and the moldability is deteriorated.

A known curing accelerator may be incorporated into the epoxy resin composition of the present invention. Examples thereof include amines, imidazoles, organophosphines, Lewis acids and the like. Specifically, 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diaza- Cyclodiamine compounds such as cyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7, A compound having an intramolecular polarization obtained by adding a compound having a π bond such as an acid, a benzoquinone or a diazophenylmethane, a compound having an intramolecular polarization such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) Tertiary amines and derivatives thereof, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole, and derivatives thereof , Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine, and phosphines such as Maleic acid, benzoquinone, and diazophenylmethane, a compound having an intramolecular polarization obtained by adding a compound having a π bond such as diazophenylmethane, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutyl Tetra-substituted boronates such as tetrabutyl borate and phosphonium tetrabutyl borate, tetraphenyl boron salts such as 2-ethyl-4-methyl imidazole tetraphenyl borate and N-methyl morpholine tetraphenyl borate, And derivatives thereof. The addition amount is usually in the range of 0.2 to 10 parts by weight based on 100 parts by weight of the epoxy resin. These may be used alone or in combination.

A flame retardant is used in the epoxy resin composition of the present invention if necessary. Examples of such a flame retardant include phosphorous flame retardants such as red phosphorus and phosphoric acid compounds, nitrogen flame retardants such as triazine derivatives, phosphorus-containing flame retardants such as phosphazene derivatives, metal oxides, metal hydrides, metallocene derivatives and the like Organometallic complexes, zinc compounds such as zinc borate, zinc stannate and zinc molybdate, and among these, metal hydrates are preferable. Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, nickel hydroxide, cobalt hydroxide, iron hydroxide, tin hydroxide, zinc hydroxide, copper hydroxide and titanium hydroxide. And metal oxides such as cobalt, iron oxide, tin oxide, zinc oxide, copper oxide, and palladium oxide may be used. Magnesium hydroxide is preferable from the viewpoints of safety, flame retardant effect, and impact on moldability of a molding material.

The epoxy resin composition of the present invention may further contain, in addition to the above components, releasing agents such as higher fatty acids, higher fatty acid metal salts, ester waxes and polyolefin waxes, coloring agents such as carbon black, coupling agents such as silane series, titanate series and aluminate series, A flexural agent such as a powder, a stress relieving agent such as a silicone oil or a silicone rubber powder, an ion trap agent such as hydrotalcite, antimony-bismuth and the like can be used as needed.

In addition, thermoplastic (thermoplastic) oligomers may be added to the epoxy resin composition of the present invention from the viewpoint of improving the fluidity at the time of molding and improving the adhesion with a substrate such as a lead frame. Examples of the thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene · styrene copolymer resins, indene · styrene · phenol copolymer resins, indene · coumarone copolymer resins and indene · benzothiophene copolymer resins . The addition amount is usually in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

Any method may be used as long as the various raw materials can be uniformly dispersed and mixed. However, as a general method, after a predetermined amount of raw materials are thoroughly mixed by a mixer or the like, a mixing roll, an extruder And the like, followed by cooling and pulverizing.

The epoxy resin composition of the present invention is particularly suitable for encapsulation in semiconductor devices.

The cured product of the present invention is obtained by thermosetting the epoxy resin composition. In order to obtain a cured product using the epoxy resin composition of the present invention, for example, transfer molding, press molding, cast molding, injection molding, extrusion molding and the like are applied, but transfer molding is preferable from the viewpoint of mass production.

Hereinafter, the present invention will be described in more detail with reference to Examples.

(Synthesis Example 1)

186.0 g (1.0 mole) of 4,4'-dihydroxybiphenyl and 600 g of diethylene glycol dimethyl ether were placed in a 2000 ml four-necked flask, and the temperature was raised to 150 ° C while stirring in a nitrogen stream, A solution prepared by dissolving 75.3 g (0.3 mol) of 4,4'-bischloromethylbiphenyl in 260 g of ethylene glycol dimethyl ether was added dropwise, and the mixture was heated to 170 ° C and reacted for 2 hours. After the reaction, a large amount of pure water was added dropwise and recovered by refluxing to obtain 220 g of a light yellow crystalline resin. The OH equivalent of the obtained resin was 130.8. The peak temperature in the DSC measurement was 248.5 占 폚, and the heat absorption amount accompanying the melting of the crystal was 95.5 J / g. A GPC chart of the obtained resin is shown in Fig. The composition ratios in the general formula (3) obtained by GPC measurement were 39.33% for n = 0, 22.25% for n = 1, 12.19% for n = 2, 8.14% for n = 3, 5.58% n? 5 was 11.88%. Here, the DSC peak temperature is a value measured at a heating rate of 5 캜 / minute using a differential scanning calorimeter (DSC220C model, Seiko Instruments Inc.). In addition, the GPC measurement can be performed using a device; Model 515A, product of Nihon Waters Corporation, column; TSK-GEL2000x3 and TSK-GEL4000x1 (all manufactured by Tosoh Corporation), solvent; Tetrahydrofuran, flow rate; 1 ml / min, temperature; 38 캜, detector; I followed the terms of RI.

(Synthesis Example 2)

(0.9 mole) of 4,4'-dihydroxybiphenyl, 540 g of diethylene glycol dimethyl ether and 90.4 g (0.36 mole) of 4,4'-bischloromethylbiphenyl were dissolved in 320 g of diethylene glycol dimethyl ether Was used in place of the solution obtained in Example 1, 205 g of a light yellow crystalline resin was obtained. The OH equivalent of the obtained resin was 139.2. The DSC peak temperature was 242.4 캜. The composition ratios in the general formula (3) obtained by GPC measurement were 31.21% for n = 0, 21.19% for n = 1, 13.38% for n = 2, 10.63% , 7.55% for n = 4, and 15.35% for n? 5.

(Synthesis Example 3)

(1.0 mol) of 4,4'-dihydroxybiphenyl, 540 g of diethylene glycol dimethyl ether and 50.2 g (0.2 mol) of 4,4'-bischloromethylbiphenyl were dissolved in 320 g of diethylene glycol dimethyl ether Was used in place of the solution obtained in Example 1, 195 g of a pale yellow crystalline resin was obtained. The OH equivalent of the obtained resin was 125.6. The DSC peak temperature was 255.4 占 폚. The component ratios in the general formula (3) obtained by GPC measurement were 50.87% for n = 0, 20.67% for n = 1, 11.54% for n = 2, 7.11% , n = 4 was 3.78%, and n? 5 was 5.87%.

(Synthesis Example 4)

152.5 g (0.82 mol) of 4,4'-dihydroxybiphenyl, 500 g of diethylene glycol dimethyl ether and 112.9 g (0.45 mol) of 4,4'-bischloromethylbiphenyl were dissolved in 360 g of diethylene glycol dimethyl ether Was used in place of the solution obtained in Example 1, to obtain 201 g of a pale yellow resin. The OH equivalent of the obtained resin was 150.1. The component ratios in the general formula (3) obtained by GPC measurement were 22.03% for n = 0, 14.65% for n = 1, 11.89% for n = 2, 9.46% for n = 3, 7.36% n? 5 was 33.87%.

(Synthesis Example 5)

A solution obtained by dissolving 186.0 g (1.0 mole) of 4,4'-dihydroxybiphenyl, 600 g of diethylene glycol dimethyl ether and 52.5 g (0.3 mole) of 1,4-bischloromethylbenzene in 260 g of diethylene glycol dimethyl ether The reaction was carried out in the same manner as in Example 1 except for using the same, to obtain 202 g of a light yellow crystalline resin. The OH equivalent of the obtained resin was 116.3. The DSC peak temperature is 241.7 ° C. In the general formula (3) obtained by GPC measurement, each component ratio corresponding to the structure in which the biphenylene group in the crosslinking site is substituted with phenylene group is n = 0 is 40.33%, n = 1 23.31%, n = 2 was 11.22%, n = 3 was 7.09%, n = 4 was 5.17% and n≥5 was 12.35%.

(Synthesis Example 6)

Except that 200.0 g (1.0 mole) of 4,4'-dihydroxydiphenylmethane was used instead of 4,4'-dihydroxybiphenyl (1.0 mole), and the reaction was carried out in the same manner as in Synthesis Example 1, The solvent was distilled off by distillation to obtain 245 g of a pale brown resin. The OH equivalent of the obtained resin was 137.6. In the structure in which the 4,4'-dihydroxybiphenyl skeleton is substituted with 4,4'-dihydroxydiphenylmethane in the general formula (3) obtained by GPC measurement, the respective component ratios of n = 0 are 36.89% , n = 1 was 20.36%, n = 2 was 12.30%, n = 3 was 9.68%, n = 4 was 6.58%, and n≥5 was 13.56%.

(Example 1)

120 g of the resin obtained in Synthesis Example 1 was dissolved in 509 g of epichlorohydrin and 76.4 g of diethylene glycol dimethyl ether and 76.5 g of 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 for 4 hours under reduced pressure (about 130 Torr). The resulting water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, 971 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 19.3 g of a 24% aqueous solution of sodium hydroxide was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, filtration and washing were carried out. Then, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 148 g of an epoxy resin (epoxy resin A). The epoxy equivalent was 183.7 and the hydrolyzable chlorine was 1400 ppm. A GPC chart of the obtained resin is shown in Fig. The composition ratios in the general formula (1) obtained by GPC measurement were 42.49% for n = 0, 19.41% for n = 1, 12.23% for n = 2, 8.50% for n = n? 5 was 8.18%. The results of the DSC measurement are shown in Fig. The peak temperature in the DSC measurement result was 140.0 占 폚, and the heat absorption amount accompanying the melting of the crystal was 36.9 J / g. The melting point of the capillary was 111.5 to 143.8 占 폚, and the melt viscosity at 150 占 폚 was 51 mPa 占 퐏.

(Example 2)

122 g of the resin obtained in Synthesis Example 2 was dissolved in 486 g of epichlorohydrin and 72.9 g of diethylene glycol dimethyl ether and 73.0 g of 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 under reduced pressure (about 130 Torr) for 4 hours. The water thus formed was removed from the system by azeotropy with epichlorohydrin, and the leached epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, 970 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 19.3 g of a 24% aqueous solution of sodium hydroxide was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 146 g of an epoxy resin (epoxy resin B). The epoxy equivalent was 195.1 and the hydrolyzable chlorine was 715 ppm. The peak temperature in the DSC measurement was 135.1 占 폚, and the heat absorption amount accompanying the melting of the crystal was 29.8 J / g. The capillary melting point was 107.8 to 140.1 ° C, and the melt viscosity at 150 ° C was 95 mPa · s. The component ratios in the general formula (1) obtained by GPC measurement were 32.25% for n = 0, 18.42% for n = 1, 12.85% for n = 2, 9.42% for n = 3, 6.01% n &ge; 5 was 16.63%.

(Example 3)

110 g of the resin obtained in Synthesis Example 3 was dissolved in 486 g of epichlorohydrin and 71.5 g of diethylene glycol dimethyl ether and 70.8 g of a 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 under reduced pressure (about 130 Torr) for 4 hours. The water thus formed was removed from the system by azeotropy with epichlorohydrin, and the leached epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Then, epichlorohydrin was distilled off, 972 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 15.5 g of a 24% aqueous sodium hydroxide solution was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, filtration and washing were carried out, and methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 149 g of an epoxy resin (epoxy resin C). The epoxy equivalent was 182.4, and the hydrolyzable chlorine was 675 ppm. The peak temperature in the DSC measurement was 146.1 占 폚, and the heat absorption amount accompanying the melting of the crystal was 46.1 J / g. The capillary melting point was 118.2 to 147.0 ° C, and the melt viscosity at 150 ° C was 36 mPa · s. The composition ratios in the general formula (1) obtained by GPC measurement were 49.16% for n = 0, 20.11% for n = 1, 10.52% for n = 2, 6.51% for n = 3, 3.98% n? 5 was 6.65%.

(Comparative Example 1)

125 g of the resin obtained in Synthesis Example 4 was dissolved in 462 g of epichlorohydrin and 69.3 g of diethylene glycol dimethyl ether and 69.4 g of a 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 under reduced pressure (about 130 Torr) for 4 hours. The water thus formed was removed from the system by azeotropy with epichlorohydrin, and the leached epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Then, epichlorohydrin was distilled off, 972 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 19.3 g of a 24% aqueous solution of sodium hydroxide was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, filtration and washing were carried out. Then, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 148 g of an epoxy resin (epoxy resin D). The epoxy equivalent was 209.2 and the hydrolyzable chlorine was 621 ppm. The crystallinity of the obtained resin was low and no definite melting point was observed by DSC. The melt viscosity at 150 ° C was 0.52 Pa · s. The composition ratios in the general formula (1) obtained by GPC measurement were 20.75% for n = 0, 12.48% for n = 1, 10.59% for n = 2, 8.57% for n = 3, 5.99% n? 5 was 37.11%.

(Comparative Example 2)

115 g of the resin obtained in Synthesis Example 5 was dissolved in 549 g of epichlorohydrin and 82.4 g of diethylene glycol dimethyl ether and 82.4 g of 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 under reduced pressure (about 130 Torr) for 4 hours. The water thus formed was removed from the system by azeotropy with epichlorohydrin, and the leached epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, 966 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 19.2 g of a 24% aqueous solution of sodium hydroxide was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, filtration and washing were carried out. Then, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 145 g of an epoxy resin (epoxy resin E). The epoxy equivalent was 173.0 and the hydrolyzable chlorine was 490 ppm. The peak temperature in the DSC measurement was 133.6 占 폚, and the heat absorption amount accompanying the melting of the crystal was 47.6 J / g. The capillary melting point was 110.0 to 142.0 占 폚, and the melt viscosity at 150 占 폚 was 42 mPa 占 퐏. The composition ratios in the general formula (1) obtained by GPC measurement were 42.92% for n = 0, 19.64% for n = 1, 11.46% for n = 2, 7.67% for n = 3, 4.91% n? 5 was 10.64%.

(Comparative Example 3)

120 g of the resin obtained in Synthesis Example 6 was dissolved in 484 g of epichlorohydrin and 62.9 g of diethylene glycol dimethyl ether and 69.0 g of 48% sodium hydroxide aqueous solution was added dropwise at 62 캜 under reduced pressure (about 130 Torr) for 4 hours. The water thus formed was removed from the system by azeotropy with epichlorohydrin, and the leached epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, 956 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 17.6 g of a 24% aqueous solution of sodium hydroxide was added, and the reaction was carried out at 85 캜 for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 152.5 g of amorphous amorphous epoxy resin (epoxy resin F). The epoxy equivalent was 193.5, and the hydrolyzable chlorine was 450 ppm. The softening point was 82 ° C, and the melt viscosity at 150 ° C was 68 mPa · s. In the structure in which the 4,4'-dihydroxybiphenyl skeleton is substituted with 4,4'-dihydroxydiphenylmethane in the general formula (1) obtained by GPC measurement, the respective component ratios of the n = 0 are 34.54% , 18.65% for n = 1, 12.34% for n = 2, 10.69% for n = 3, 8.20% for n = 4 and 15.22% for n≥5.

(Examples 4 to 6 and Comparative Examples 4 to 7)

(Epoxy resins A to C) of Examples 1 to 3 and epoxy resins (epoxy resins D to F) of Comparative Examples 1 to 3 were used as epoxy resin components and phenol novolak Product, PSM-4261, OH equivalent 103, softening point 82 캜) was used. Also, triphenylphosphine was used as a curing accelerator, and spherical alumina (average particle diameter: 12.2 탆) was used as an inorganic filler. The components shown in Table 1 were compounded, mixed thoroughly with a mixer, and mixed and kneaded with a heating roll for about 5 minutes. The mixture was cooled and pulverized to obtain epoxy resin compositions of Examples 4 to 6 and Comparative Examples 4 to 7, respectively. This epoxy resin composition was molded at 175 DEG C for 5 minutes, and post cured at 180 DEG C for 12 hours to obtain a cured molded article, and the properties thereof were evaluated.

The results are summarized in Table 1. Also, the number of each compound in Table 1 represents parts by weight. The evaluation was carried out as follows. Also, in Comparative Example 4, since the fluidity was remarkably low and molding was difficult, the properties of the molded article could not be evaluated.

(1) Thermal conductivity: Measured by a non-constant heat ray method using a NETZSCH LFA447 thermal conductivity meter.

(2) Coefficient of linear expansion and glass transition temperature: Measured at a heating rate of 10 캜 / minute using a thermomechanical measuring instrument of TMA120C manufactured by Seiko Instruments.

(3) Water absorption rate: A disk having a diameter of 50 mm and a thickness of 3 mm was molded, post cured, and the weight change rate after moisture absorption at 85 캜 and 85% relative humidity for 100 hours was determined.

(4) Gel time: The epoxy resin composition was poured into a concave portion of a gelation tester (manufactured by Nisshin Kagaku Co., Ltd.) preliminarily heated to 175 ° C, and a rotation speed of two revolutions per second , And the gelation time required until the epoxy resin composition hardened was investigated.

(5) Spiral flow: A mold for spiral flow measurement conforming to the specification (EMMI-1-66) was prepared under the conditions of injection pressure of spiral flow (150 kgf / cm ² ), curing temperature of 175 캜, curing time of 3 minutes To investigate the flow length.

Since the epoxy resin of the present invention has a crystalline melting point, it is excellent in handleability as a solid, has excellent moldability because of its low viscosity, and has excellent heat resistance, thermal decomposition stability, and high thermal conductivity It is possible to use this excellent hardened material to suitably use for the sealing of electric / electronic parts, the material of the circuit board, and the like. Further, the epoxy resin obtained by the present invention is excellent in handleability as a low viscosity and solid, and is also excellent in heat resistance, moisture resistance, and thermal conductivity, and is excellent in electrical insulation in electrical and electronic fields such as printed wiring boards, Materials and the like.

Claims

(1)

(Wherein n represents an average value of 0.2 to 4.0, and G represents a glycidyl group.)
Lt; / RTI >
0.1 to 0.4 mol of a biphenyl-based condensing agent represented by the following general formula (2) is reacted with 1 mol of 4,4'-dihydroxybiphenyl to obtain a polyhydric hydroxy resin represented by the following general formula (3) And an epichlorohydrin. The epoxy resin has crystallinity such that the endothermic peak temperature based on the melting point in the differential scanning calorimetry is in the range of 100 to 150 ° C.

(Where n represents an average value of 0.2 to 4.0).

delete

The epoxy resin according to claim 1, wherein the content of n = 0 in the general formula (1) is in the range of 30 to 60%.

The epoxy resin according to claim 1, wherein the epoxy resin has a softening point of 100 to 150 ° C and a melt viscosity at 150 ° C of 0.02 to 0.2 Pa · s.

An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin component contains the epoxy resin according to any one of claims 1 to 3.

A cured product obtained by curing the epoxy resin composition according to claim 5.