KR20120115301A - Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product - Google Patents

Abstract

Provides an epoxy resin, an epoxy resin composition using the same, and a cured product having excellent performance in low viscosity and solidity, as well as excellent heat resistance, moisture resistance, and thermal conductivity, and are useful for lamination, molding, molding, and adhesion. .
The epoxy resin of this invention is represented by following General formula (1), and is an epoxy resin which has the crystallinity which the endothermic peak temperature based on melting | fusing point in differential scanning calorimetry is in the range of 100-150 degreeC. Moreover, the epoxy resin composition of this invention is an epoxy resin composition containing this epoxy resin and a hardening | curing agent as an essential component. In General formula (1), n represents 0.2-4.0 as an average value, G represents a glycidyl group.

Description

Epoxy resin, manufacturing method thereof, epoxy resin composition and cured product using the same {EPOXY RESIN, PROCESS FOR PRODUCTION THEREOF, EPOXY RESIN COMPOSITION USING SAME, AND CURED PRODUCT}

The present invention relates to a crystalline epoxy resin, a production method thereof, an epoxy resin composition and a cured product using the same.

In recent years, with the progress in the field of advanced materials in particular, the development of higher performance base resins is required. For example, in the field of semiconductor encapsulation, the base resin excellent in high heat resistance and thermal decomposition stability is calculated | required by the advancement of the semiconductor for vehicles. On the other hand, since high density mounting is also advanced, high filling rate of inorganic filler is aimed at, and the low viscosity of base resin is also strongly demanded. Moreover, the improvement of the high temperature reliability to respond to severe use environment is calculated | required, and the improvement of thermal conductivity is also calculated | required from the viewpoint of heat dissipation improvement.

However, conventionally known epoxy resins have not been found to satisfy these requirements. For example, although naphthol aralkyl type epoxy resin is proposed in Patent Document 1 as being excellent in heat resistance and moisture resistance, it is not sufficient in terms of heat resistance and high in viscosity, which is not suitable for high filling rate of the inorganic filler. Moreover, although excellent in heat resistance, patent document 2 discloses the aralkyl type epoxy resin which connected 4,4'- dihydroxy biphenyl to p-xylylene group, but there exists a problem in moisture resistance and a flame retardance. Patent Document 3 discloses a biphenyl aralkyl type epoxy resin having a structure in which a bisphenol compound is linked to a biphenylene group, but is a resinous material having no crystallinity, and thus has a problem in moldability due to high viscosity and softening point.

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

Accordingly, an object of the present invention is to provide an epoxy resin which is excellent in low viscosity and handleability as a solid, and also has excellent performance in heat resistance, moisture resistance, and thermal conductivity, and is useful for applications such as lamination, molding, molding, adhesion, and the like. It is providing the used epoxy resin composition and its hardened | cured material.

That is, this invention is represented by following General formula (1), and relates to the epoxy resin which has the crystallinity whose endothermic peak temperature based on melting | fusing point in differential scanning calorimetry is in the range of 100-150 degreeC.

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

Moreover, this invention reacts with 1 mol of 4,4'- dihydroxy biphenyls, 0.1-0.4 mol of the biphenyl type condensing agent represented by following General formula (2) is represented by following General formula (3). It is related with the epoxy resin which has the crystallinity which the endothermic peak temperature based on melting | fusing point in the differential scanning calorimetry obtained by making it react with this and epichlorohydrin after making it a polyhydric hydroxy resin in the range of 100-150 degreeC. .

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

(N shows 0.2-4.0 as an average value.)

Moreover, this invention relates to the epoxy resin composition which contains said epoxy resin as an epoxy resin component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, and the hardened | cured material formed by hardening it.

According to the present invention, an epoxy resin excellent in low viscosity and handleability as a solid, and excellent in heat resistance, moisture resistance, and thermal conductivity, and useful for applications such as lamination, molding, molding, and adhesion, and an epoxy resin composition using the same, Hardened | cured material can be provided.

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

Hereinafter, the present invention will be described in detail.

The epoxy resin of this invention is represented by General formula (1), and is a mixture of the component of which the value of a repeating unit (n) differs. Here, n represents 0.2-4.0 as an average value. When smaller than this, crystallinity becomes strong and melting | fusing point becomes high and handleability falls. When larger than this, crystallinity will fall and a viscosity will become high and a moldability will fall. From the viewpoint of low viscosity, handleability 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 as used herein refers to a number average value.

The epoxy resin of the present invention has crystallinity and is crystallized in a solid state. The temperature of the endothermic peak based on melting | fusing point in the differential scanning calorimetry which measured this crystalline solid at the temperature increase rate of 10 degree-C / min is 100-150 degreeC, Preferably it exists in the range of 120-150 degreeC. If higher than this, compatibility with the hardening | curing agent at the time of adjusting an epoxy resin composition will fall, and if lower than this, problems, such as blocking of an epoxy resin composition, will arise and handleability will fall. Depending on the crystalline state of the epoxy resin, there may be a plurality of peaks of the melting point, but the endothermic peak temperature here refers to the one corresponding to the largest peak. The endothermic amount of the peak is considered to indicate the degree of crystallinity, but is usually in the range of 20 to 80 J / g in terms of the resin component. If it is smaller than this, the degree of crystallinity is low and the handleability is lowered.

Although the epoxy resin of this invention is obtained by making polyhydric hydroxy resin and epichlorohydrin represented by General formula (3) react, in the invention of an epoxy resin, a manufacturing method is not limited to this. However, by explaining the invention of the production method, the understanding of the epoxy resin of the present invention is facilitated, and therefore, the method of producing the polyhydric hydroxy resin and the epoxy resin, which are the raw materials of the epoxy resin, will be described.

The polyhydric hydroxy resin represented by General formula (3) is a mixture of the components from which the value of n differs, and n is 0.2-4.0 as an average value. When smaller than this, crystallinity becomes strong, the solubility to epichlorohydrin at the time of synthesize | combining an epoxy resin falls, and melting | fusing point of the obtained epoxy resin becomes high and handleability falls. When larger than this, crystallinity will fall and a viscosity will become high and a moldability will fall. From the viewpoint of low viscosity, handleability and moldability, it is preferable that the content ratio of n = 0 is in the range of 30 to 60%.

Such polyhydric hydroxy resin is obtained by making a 4,4'- dihydroxy biphenyl react with the biphenyl type condensing agent represented by General formula (2).

In General formula (2), X represents a hydroxyl group, a halogen atom, or a C1-C6 alkoxy group. Specifically, 4,4'-bishydroxymethyl biphenyl, 4,4'-bischloromethyl biphenyl, 4,4'-bisbromomethyl biphenyl, 4,4'-bismethoxymethyl biphenyl And 4,4'-bisethoxymethylbiphenyl. 4,4'-bishydroxymethylbiphenyl and 4,4'-bischloromethylbiphenyl are preferable from a reactive viewpoint, and 4,4'-bishydroxy from a viewpoint of ionic impurity reduction. Methyl biphenyl and 4,4'-bismethoxymethylbiphenyl are preferable.

The molar ratio at the time of reaction should be 1 mol or less of biphenyl type condensing agents with respect to 1 mol of 4,4'- dihydroxy biphenyls, Generally it is the range of 0.1-0.5 mol, More preferably, It is the range of 0.2-0.4 mol. When less than this, crystallinity becomes strong, the solubility to epichlorohydrin at the time of synthesize | combining an epoxy resin falls, and melting | fusing point of the obtained epoxy resin becomes high and handleability falls. If more than this, the crystallinity of the resin decreases, and the softening point and the melt viscosity increase, resulting in problems in handling workability and moldability.

In addition, when 4,4'-bischloromethyl biphenyl is used as a condensing agent, although it can also react without a catalyst, this condensation reaction is normally performed in presence of an acidic catalyst. As this acidic catalyst, it can select suitably from well-known inorganic acid and organic acid, For example, mineral acid, such as hydrochloric acid, a sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, metasulfonic acid, Organic acids such as trifluoromethsulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, and solid acids.

This reaction is performed at 10-250 degreeC for 1 to 20 hours. In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent. After completion | finish of reaction, the solvent and water and alcohols produced by condensation reaction are removed as needed.

The polyhydric hydroxy resin obtained in this way can be used also as an epoxy resin hardening | curing agent, in addition to being used as a raw material of an epoxy resin. Moreover, it can be applied also as a phenol resin molding material by further combining with hardening | curing agents, such as hexamine.

The manufacturing method of the epoxy resin of this invention by reaction of polyhydric hydroxy resin and epichlorohydrin represented by General formula (3) is demonstrated. This reaction can be performed similarly to a well-known epoxidation reaction.

For example, after melt | dissolving the polyhydric hydroxy resin represented by General formula (3) in excess epichlorohydrin, it is 50-150 degreeC in presence of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, Preferably it is 60- The method of making it react for 1 to 10 hours in the range of 120 degreeC is mentioned. The usage-amount of epichlorohydrin at this time is 0.8-2 mol with respect to 1 mol of hydroxyl groups in polyhydric hydroxy resin, Preferably it is the range of 0.9-1.2 mol. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off. The epoxy resin of the objective represented by (1) can be obtained. When performing an epoxidation reaction, you may use catalysts, such as a quaternary ammonium salt.

The purity of the epoxy resin of the present invention, particularly the amount of hydrolyzable chlorine, is preferably less from the viewpoint of improving the reliability of the electronic component to be applied. Although not specifically limited, Preferably it is 1000 ppm or less, More preferably, it is 500 ppm or less. In addition, the hydrolysable chlorine used by this invention means the value measured by the following method. That is, 0.5 g of the sample was dissolved in 30 ml of dioxane, 1 ml of 1N-KOH and 10 ml were added thereto, and the mixture was refluxed for 30 minutes. After cooling to room temperature, 100 ml of 80% acetone water was added, followed by 0.002N-AgNO. _It is a value obtained by performing potentiometric titration with ₃ aqueous solution.

The epoxy resin composition of this invention contains an epoxy resin and a hardening | curing agent, and contains the epoxy resin of the said General formula (1) as an epoxy resin component.

In addition to the epoxy resin of General formula (1) used as an essential component, the epoxy resin composition of this invention may use together another ordinary epoxy resin which has 2 or more epoxy groups in a molecule | numerator. For example, bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 4,4 '-Dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, fluorenebisphenol, 4,4'-biphenol, 3,3', 5,5'-tetramethyl-4,4 '-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 And divalent compounds such as allyl or polyallylate of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, and allylated phenol novolac Phenols or phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxy styrene, tris- (4-hydride Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, Trivalent or more phenols such as 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, or tetrabromobisphenol Glycidyl ether derivatives derived from halogenated bisphenols such as A and the like. These epoxy resins can be used 1 type or in mixture of 2 or more types.

It is preferable that the epoxy resin composition of this invention contains 50 weight% or more of epoxy resin components of the said General formula (1) as an epoxy resin. More preferably, it is 70 wt% or more of the whole epoxy resin, More preferably, it is 80 wt% or more. When the use ratio is less than this, the moldability as an epoxy resin composition deteriorates, and the improvement effect, such as heat resistance, moisture resistance, heat conductivity, and solder reflow resistance, when making hardened | cured material is small.

As a hardening | curing agent in the epoxy resin composition of this invention, what is generally known as a hardening | curing agent of an epoxy resin 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 encapsulation of electrical and electronic components requiring moisture resistance and heat resistance. Specific examples of these are as follows. 1 type (s) or 2 or more types of these hardening | curing agents can be mixed and used for the resin composition of this invention.

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

Examples of the acid anhydride include phthalic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, methyl hyalic anhydride, nadic acid anhydride, trimellitic anhydride and the like.

As amines, aromatics, such as 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl propane, 4,4'- diamino diphenyl sulfone, m-phenylenediamine, and p-xylylenediamine Aliphatic amines such as amines, ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine.

1 type (s) or 2 or more types of these hardening | curing agents can be mixed and used for the resin composition of this invention.

In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyphenylene ether, polyurethane, petroleum resin, indencoumarone resin, and phenoxy resin may be appropriately blended. You may mix | blend various additives, such as an inorganic filler, a pigment, a flame retardant, a thixotropic agent, a coupling agent, and a fluidity improving agent.

In the epoxy resin composition of the present invention, an inorganic filler can be blended, for example, silica powder such as spherical or crushed fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide Powders such as boron nitride, beryllia, zirconia, forsterite, steatite, spinel, mullite, titania, or beads having spherical shape, potassium titanate, silicon carbide, silicon nitride, alumina Single crystal fiber, glass fiber, etc., such as these, can be used individually or in combination of 2 or more types. Among the inorganic fillers described above, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. It is preferable that the filler shape is spherical from 50% or more in terms of fluidity and mold wearability at the time of molding, and it is particularly preferable to use spherical fused silica powder.

The amount of the inorganic filler added is usually 50 wt% or more with respect to the epoxy resin composition, but is preferably 70 wt% or more, more preferably 80 wt% or more. When less than this, the effect aimed at by this invention, such as low hygroscopicity, low thermal expansion, high heat resistance, and high thermal conductivity, is not fully exhibited. Although these effects are so good that the addition amount of an inorganic filler is large, it does not improve according to the volume fraction, but improves dramatically from a specific addition amount. On the other hand, when the addition amount of an inorganic filler is larger than this, since a viscosity becomes high and moldability deteriorates, it is unpreferable.

A well-known hardening accelerator can be mix | blended with the epoxy resin composition of this invention. For example, there are amines, imidazoles, organic phosphines, Lewis acids, and the like, specifically 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diaza-r Cycloamidine compounds such as cyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and maleic anhydride in these compounds Compounds having intramolecular polarization by adding compounds having π bonds such as acids, benzoquinones and diazophenylmethane, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Tertiary amines and derivatives thereof, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and derivatives thereof Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine and phosphine thereof Phosphorus compounds having an intramolecular polarization formed by adding compounds having a π bond such as maleic acid, benzoquinone, and diazophenylmethane, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate and tetrabutyl Tetraphenyl boron salts, such as tetra substituted phosphonium tetra substituted borate, 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, such as phosphonium tetrabutyl borate, and these Derivatives; and the like. As addition amount, it is the range of 0.2-10 weight part with respect to 100 weight part of epoxy resins normally. These may be used independently and may be used together.

A flame retardant is used for the epoxy resin composition of this invention as needed. Such flame retardants include, for example, phosphorus flame retardants such as red phosphorus and phosphoric acid compounds, nitrogen flame retardants such as triazine derivatives, phosphate flame retardants such as phosphazene derivatives, metal oxides, metal hydrates, metallocene derivatives, and the like. Zinc compounds, such as an organometallic complex, zinc borate, zinc stannate, and zinc molybdate, etc. are mentioned, A metal hydrate is especially 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, titanium hydroxide, and the like, and these metal hydrates, nickel oxide, and oxides. Complex metal hydrates with metal oxides such as cobalt, iron oxide, tin oxide, zinc oxide, copper oxide, palladium oxide and the like can be used. Magnesium hydroxide is preferred from the viewpoint of the safety, the flame retardant effect and the influence on the formability of the molding material.

In the epoxy resin composition of the present invention, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, and polyolefin waxes, colorants such as carbon black, coupling agents such as silanes, titanates, and aluminates, and silicones Flexible agents such as powders, stress relieving agents such as silicone oils and silicone rubber powders, and ion trapping agents such as hydrotalcyto and antimony-bismuth may be used as necessary.

In addition, thermoplastic oligomers can be added to the epoxy resin composition of the present invention from the viewpoint of improving fluidity during molding and improving adhesion to substrates such as lead frames. Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene styrene copolymer resins, indene styrene copolymers, indene coumarone copolymer resins, and indene benzothiophene copolymer resins. Is illustrated. As addition amount, it is the range of 2-30 weight part with respect to 100 weight part of epoxy resins normally.

The method for preparing the epoxy resin composition of the present invention may be any method as long as it can uniformly disperse and mix various raw materials, but as a general method, after sufficiently mixing the raw materials having a predetermined compounding amount by a mixer or the like, a mixing roll and an extruder And the like may be melt mixed and kneaded, cooled and pulverized.

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

The hardened | cured material of this invention is obtained by thermosetting the said epoxy resin composition. In order to obtain hardened | cured material using the epoxy resin composition of this invention, methods, such as transfer molding, press molding, casting molding, injection molding, extrusion molding, are applied, for example, but transfer molding is preferable from a mass productivity viewpoint.

<Examples>

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

(Synthesis Example 1)

Into a 2000 ml four-necked flask, 186.0 g (1.0 mol) of 4,4'-dihydroxybiphenyl and 600 g of diethylene glycol dimethyl ether were added, and the temperature was raised to 150 ° C while stirring under a stream of nitrogen, and di The solution which melt | dissolved 75.3 g (0.3 mol) of 4,4'-bischloromethyl biphenyls was dripped at 260 g of ethylene glycol dimethyl ether, and it heated up to 170 degreeC and made it react for 2 hours. After the reaction, the mixture was dropped into a large amount of pure water and recovered by reprecipitation to obtain 220 g of a pale yellow crystalline resin. OH equivalent of obtained resin was 130.8. The peak temperature in DSC measurement was 248.5 degreeC, and the endothermic amount accompanying melting of the crystal | crystallization was 95.5 J / g. The GPC chart of obtained resin is shown in FIG. In the formula (3) determined by the GPC measurement, each component ratio in n = 39.33%, n = 1 22.25%, n = 2 12.19%, n = 3 8.14%, n = 4 5.58%, n ≧ 5 was 11.88%. Here, DSC peak temperature is the value measured at the temperature increase rate of 5 degree-C / min using the differential scanning calorimetry apparatus (Seiko Instruments DSC220C type | mold). GPC measurements also include devices; Nihon Waters Co., Ltd., Form 515A, Column; TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corporation), solvent; Tetrahydrofuran, flow rate; 1 ml / min, temperature; 38 ° C., detector; Followed the terms of RI.

(Synthesis Example 2)

167.4 g (0.9 mol) of 4,4'-dihydroxybiphenyl, 540 g of diethylene glycol dimethyl ether, and 90.4 g (0.36 mol) of 4,4'-bischloromethyl biphenyl were dissolved in 320 g of diethylene glycol dimethyl ether. Except having used the solution, it reacted similarly to Example 1 and obtained 205g of pale yellow and crystalline resin. OH equivalent of obtained resin was 139.2. The DSC peak temperature is 242.4 ° C, and the component ratios in the general formula (3) determined by GPC measurement are n = 31.21%, n = 1 21.19%, n = 2 13.38%, and n = 3 10.63% , n = 4 was 7.55% and n ≧ 5 was 15.35%.

(Synthesis Example 3)

186.0 g (1.0 mol) of 4,4'- dihydroxy biphenyl, 540 g of diethylene glycol dimethyl ether, and 50.2 g (0.2 mol) of 4,4'-bischloromethyl biphenyl were dissolved in 320 g of diethylene glycol dimethyl ether. Except having used the solution, it reacted like Example 1 and obtained 195 g of pale yellow crystalline resin. OH equivalent of obtained resin was 125.6. DSC peak temperature is 255.4 degreeC, and each component ratio in General formula (3) calculated | required by GPC measurement has n = 50.87%, n = 1 is 20.67%, n = 2 is 11.54%, n = 3 is 7.11% , n = 4 was 3.78% and n ≧ 5 was 5.87%.

(Synthesis Example 4)

152.5 g (0.82 mole) of 4,4'-dihydroxybiphenyl, 500 g of diethylene glycol dimethyl ether, and 112.9 g (0.45 mole) of 4,4'-bischloromethyl biphenyl were dissolved in 360 g of diethylene glycol dimethyl ether. The reaction was carried out in the same manner as in Example 1 except that the solution was used to obtain 201 g of a pale yellow resin. OH equivalent of obtained resin was 150.1. In the formula (3) determined by the GPC measurement, each component ratio in n = 0 was 22.03%, n = 1 14.65%, n = 2 was 11.89%, n = 3 was 9.46%, n = 4 was 7.36%, n ≧ 5 was 33.87%.

Synthesis Example 5

186.0 g (1.0 mol) of 4,4'- dihydroxy biphenyl, 600 g of diethylene glycol dimethyl ether, and 52.5 g (0.3 mol) of 1,4-bischloromethylbenzene were dissolved in 260 g of diethylene glycol dimethyl ether. Except having used, reaction was carried out similarly to Example 1, and obtained 202g of pale yellow and crystalline resin. OH equivalent of obtained resin was 116.3. DSC peak temperature is 241.7 degreeC, and in General formula (3) calculated | required by GPC measurement, each component ratio corresponding to the structure which substituted the biphenylene group of the bridge | crosslinking site by the phenylene group has n = 0 40.33% and 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)

The reaction was carried out in the same manner as in Synthesis example 1 except that 200.0 g (1.0 mole) of 4,4'-dihydroxydiphenylmethane was used instead of 4,4'-dihydroxybiphenyl (1.0 mole). The solvent was distilled off by distillation and 245 g of light brown resins were obtained. OH equivalent of obtained resin was 137.6. In the general formula (3) determined by GPC measurement, the component ratio in the structure where the 4,4'-dihydroxybiphenyl skeleton was substituted with 4,4'-dihydroxydiphenylmethane was n = 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 an aqueous 48% sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the released epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. Then, epichlorohydrin was distilled off and 971 g of methyl isobutyl ketones were added, and salt was removed by water washing. Thereafter, 19.3 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C 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 148 g of epoxy resin (epoxy resin A). Epoxy equivalent was 183.7 and hydrolysable chlorine was 1400 ppm. The GPC chart of obtained resin is shown in FIG. In the formula (1) determined by the GPC measurement, the component ratios of n = 42.49%, n = 1 19.41%, n = 2 12.23%, n = 3 8.50%, n = 4 4.56%, n ≧ 5 was 8.18%. The DSC measurement result is shown in FIG. The peak temperature in the DSC measurement result was 140.0 degreeC, and the endothermic amount accompanying melting of the crystal | crystallization was 36.9 J / g. Moreover, capillary melting | fusing point was 111.5-143.8 degreeC, and melt viscosity in 150 degreeC was 51 mPa * s.

(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 an aqueous 48% sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. Thereafter, epichlorohydrin was distilled off, and after adding 970 g of methyl isobutyl ketones, the salt was removed by water washing. Thereafter, 19.3 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C 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 epoxy resin (epoxy resin B). Epoxy equivalent was 195.1 and hydrolysable chlorine was 715 ppm. The peak temperature in DSC measurement was 135.1 degreeC, and the endothermic amount accompanying melting of the crystal | crystallization was 29.8 J / g. Capillary melting | fusing point was 107.8-140.1 degreeC, and melt viscosity in 150 degreeC was 95 mPa * s. In the formula (1) determined by the GPC measurement, each component ratio in n = 32.25%, n = 1 18.42%, n = 2 12.85%, n = 3 9.42%, n = 4 6.01%, n ≧ 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 an aqueous 48% sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. Thereafter, epichlorohydrin was distilled off, and after adding 972 g of methyl isobutyl ketones, the salt was removed by water washing. Thereafter, 15.5 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone, which was a solvent, was distilled off under reduced pressure to obtain 149 g of epoxy resin (epoxy resin C). Epoxy equivalent was 182.4 and hydrolysable chlorine was 675 ppm. The peak temperature in DSC measurement was 146.1 degreeC, and the endothermic amount accompanying melting of the crystal | crystallization 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. In the formula (1) determined by the GPC measurement, the component ratios of n = 49.16%, n = 1 20.11%, n = 2 10.52%, n = 3 6.51%, n = 4 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% aqueous sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. Thereafter, epichlorohydrin was distilled off, and after adding 972 g of methyl isobutyl ketones, the salt was removed by water washing. Thereafter, 19.3 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone, which was a solvent, was distilled off under reduced pressure to obtain 148 g of epoxy resin (epoxy resin D). Epoxy equivalent was 209.2 and hydrolysable chlorine was 621 ppm. The crystallinity of the obtained resin was low and no clear melting point was recognized in DSC. Melt viscosity in 150 degreeC was 0.52 Pa.s. In the formula (1) determined by the GPC measurement, each component ratio of n = 20.75%, n = 1 12.48%, n = 2 10.59%, n = 3 8.57%, n = 4 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 an aqueous 48% sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. After that, epichlorohydrin was distilled off and 966 g of methyl isobutyl ketones were added, and the salt was removed by water washing. Thereafter, 19.2 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone, which was a solvent, was distilled off under reduced pressure to obtain 145 g of epoxy resin (epoxy resin E). Epoxy equivalent was 173.0 and hydrolysable chlorine was 490 ppm. The peak temperature in DSC measurement was 133.6 ° C, and the endothermic amount accompanying melting of the crystal was 47.6 J / g. The capillary melting point was 110.0-142.0 degreeC, and melt viscosity in 150 degreeC was 42 mPa * s. In the formula (1) determined by the GPC measurement, each component ratio in n = 0 is 42.92%, n = 1 is 19.64%, n = 2 is 11.46%, n = 3 is 7.67%, n = 4 is 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 an aqueous 48% sodium hydroxide solution was added dropwise at 62 ° C under reduced pressure (about 130 Torr) for 4 hours. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. The reaction was continued for 1 hour after the completion of dropping. After that, epichlorohydrin was distilled off and 956 g of methyl isobutyl ketones were added, and the salt was removed by water washing. Thereafter, 17.6 g of an aqueous 24% sodium hydroxide solution was added, and the mixture was reacted at 85 ° C for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone, which was a solvent, was distilled off under reduced pressure to obtain 152.5 g of a light brown amorphous epoxy resin (epoxy resin F). Epoxy equivalent was 193.5 and hydrolysable chlorine was 450 ppm. The softening point was 82 ° C, and the melt viscosity at 150 ° C was 68 mPa · s. In the structure where the 4,4'-dihydroxybiphenyl skeleton was substituted with 4,4'-dihydroxydiphenylmethane in the general formula (1) determined by GPC measurement, each component ratio of n = 0 was 34.54%. , n = 1 was 18.65%, n = 2 was 12.34%, n = 3 was 10.69%, n = 4 was 8.20%, and n ≧ 5 was 15.22%.

(Examples 4-6, Comparative Examples 4-7)

As the epoxy resin component, epoxy resins (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 phenol novolacs (Gunei Chemical Co., Ltd.). Product, PSM-4261; OH equivalent 103, softening point 82 占 폚). Moreover, triphenylphosphine was used as a hardening accelerator, and spherical alumina (average particle diameter 12.2 micrometers) was used as an inorganic filler. After mix | blending the component shown in Table 1, and fully mixing with a mixer, the thing knead | mixed and kneaded for about 5 minutes with the heating roll was cooled, it grind | pulverized, and the epoxy resin composition of Examples 4-6 and Comparative Examples 4-7 was obtained, respectively. Using this epoxy resin composition, after shaping | molding on the conditions of 175 degreeC and 5 minutes, postcure was performed at 180 degreeC for 12 hours, the cured molding was obtained, and the physical property was evaluated.

The results are summarized in Table 1. In addition, the number of each compound of Table 1 shows a weight part. In addition, evaluation was performed by the following. Moreover, since the fluidity | liquidity was remarkably low in the comparative example 4, molding was not able to evaluate the physical property of the molded object.

(1) Thermal conductivity: It measured by the unsteady heat wire method using the LFA447 type | mold thermal conductivity meter made from NETZSCH.

(2) Linear expansion coefficient and glass transition temperature: It measured at the temperature increase rate of 10 degree-C / min using the Seiko Instruments Co., Ltd. product TMA120C type thermometer measuring apparatus.

(3) Absorption rate: The disk of diameter 50mm and thickness 3mm was shape | molded, and it was set as the weight change rate after moisture absorption for 100 hours on 85 degreeC and 85% of the relative humidity after postcure.

(4) Gel time: The epoxy resin composition was poured into the concave portion of the gelling tester (Nisshin Chemical Co., Ltd.), which had been heated to 175 ° C in advance, and the speed of two rotations per second using a stirring rod made of PTFE. After stirring, the required gelation time was investigated until the epoxy resin composition was cured.

(5) Spiral flow: Spiral flow measurement mold according to the standard (EMMI-1-66), epoxy resin composition in the spiral flow injection pressure (150kgf / cm ² ), curing temperature 175 ℃, curing time 3 minutes Molding was performed to investigate the flow length.

Since the epoxy resin of the present invention has a melting point due to its crystallinity, it has excellent handleability as a solid, low viscosity, excellent moldability, and excellent high heat resistance, thermal decomposition stability, and high thermal conductivity when applied to an epoxy resin composition. This excellent hardened | cured material can be provided and it can use suitably for uses, such as sealing of electrical and electronic components, a circuit board material. In addition, the epoxy resin obtained by the present invention provides a cured product which is excellent in low viscosity and solidity as well as excellent in heat resistance, moisture resistance, and thermal conductivity, and insulated in electric and electronic fields such as printed wiring boards, heat-dissipating substrates, and semiconductor encapsulation. It is suitably used for materials.

Claims (6)

General formula (1)

(However, n represents 0.2 to 4.0 as an average value, and G represents a glycidyl group.)
It is represented by and the endothermic peak temperature based on melting | fusing point in differential scanning calorimetry has crystallinity in the range of 100-150 degreeC, The epoxy resin characterized by the above-mentioned. With respect to 1 mol of 4,4'- dihydroxy biphenyls, 0.1-0.4 mol of the biphenyl-type condensing agent represented by following General formula (2) is made to react, and it is polyhydric hydroxy resin represented by following General formula (3). The endothermic peak temperature based on melting | fusing point in the differential scanning calorimetry obtained by making this and epichlorohydrin react after making it have the crystallinity which exists in the range of 100-150 degreeC.

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

(N shows 0.2-4.0 as an average value.) The epoxy resin according to claim 1, wherein the content of n = 0 in General Formula (1) is in the range of 30 to 60%. The epoxy resin according to claim 1, wherein the softening point is 100 to 150 ° C and the melt viscosity at 150 ° C is in the range of 0.02 to 0.2 Pa · s. Epoxy resin composition containing an epoxy resin and a hardening | curing agent WHEREIN: The epoxy resin composition containing the epoxy resin in any one of Claims 1-4 as an epoxy resin component. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 5.

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