TW201418308A - Epoxy resin, epoxy resin composition, method for curing same, and cured product thereof - Google Patents

Abstract

Provided is an epoxy resin cured product that, whether used for lamination, molding, or casting, has excellent high heat resistance, high-temperature and long-term pyrolysis stability, and fluidity, and that is useful in the sealing of electrical and electronic parts, for circuit substrate materials, and the like. Provided are: an epoxy resin containing at least 10% of a polymer represented by general formula (2), wherein n is 1 or greater; an epoxy resin composition containing the epoxy resin, a phenolic curing agent, a curing catalyst, and an inorganic filler; and a cured product thereof. Here, R is a hydrogen atom or a C1-6 hydrocarbon group, and G is a glycidyl group.

Description

Epoxy resin, epoxy resin composition, hardening method of epoxy resin composition and hardened material

The present invention relates to an excellent epoxy resin, an epoxy resin composition, a curing method, and a cured product which are excellent in heat resistance, thermal decomposition stability, and fluidity.

Epoxy resins have been used in a wide range of applications in the industry, but their performance has been increasing in recent years. Among them, in the development of power devices in recent years, the power density of the device is required to be further increased. As a result, the surface temperature of the wafer at the time of actuation is also 250 ° C, and it is desired to develop a sealing material which can withstand the temperature.

Among them, as an epoxy resin composition excellent in heat resistance, an epoxy resin having a tetraphenylethane structure is known. For example, Patent Document 1 shows a tetraphenylethane type epoxy resin and a polyhydric phenol. The resin hardener is an epoxy resin composition which is an essential component, and an epoxy resin cured product excellent in heat resistance is disclosed. Further, Patent Document 2 discloses an epoxy resin composition and a cured product which are excellent in heat resistance of a tetraphenylethane type epoxy resin and an acid anhydride curing agent. However, when using this tetraphenylethane type epoxy resin, A cured product having a glass transition temperature of about 230 ° C cannot be obtained by a usual molding method, and in the case of using a phenol resin hardener, only a cured product having a glass transition temperature of 200 ° C or less can be obtained. Therefore, there is a problem that the characteristics of the sealing material for a high heat-resistant power device satisfying the operating temperature of a high resistance such as 250 ° C cannot be obtained.

In addition, when it is practically used at a high temperature, not only the glass transition temperature of the heat resistance index is important, but also the decomposition temperature at the time of high temperature use is important, and therefore a material having a decomposition temperature higher than the glass transition temperature is required.

[Previous Technical Literature]

[Patent Document 1] JP-A-9-3162

[Patent Document 2] JP-A-2-219812

An object of the present invention is to provide a high heat resistance, a high temperature, a long-term thermal decomposition stability, and an excellent fluidity in electrical conductivity, such as lamination, molding, injection molding, and the like. A cured epoxy resin useful for sealing electronic components and circuit board materials.

The present invention relates to an epoxy resin represented by the following general formula (2),

(here, R independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group, and n is a repeating number, and 10% or more of n is a polymer having 1 or more).

In addition, the present invention relates to an epoxy resin, the characteristics of which It is obtained by reacting a polyhydric hydroxy compound having 10% or more of a component having n = 1 or more in the area % measured by colloidal permeation chromatography with epichlorohydrin, which is represented by the following general formula (1).

The epoxy resin is preferably an epoxy resin represented by the above formula (2), and preferably contains 10% or more of a polymer in which n is 1 or more.

(wherein R independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group, and n represents a repeating number).

Further, the present invention relates to an epoxy resin composition characterized by comprising the above epoxy resin, a phenolic curing agent, a curing catalyst, and an inorganic filler.

Wherein, the hardening catalyst is preferably at least one selected from the group consisting of imidazoles, organic phosphines, or amines, and more preferably exhibits the use of DSC to measure the epoxy resin at a heating rate of 10 ° C /min. It shows the hardening performance at a high point of 150 °C or higher.

Further, the present invention relates to a method for curing an epoxy resin composition, characterized in that the epoxy resin composition is formed at 100 ° C to 200 ° C and then post-cured at 200 ° C to 300 ° C, and The cured epoxy resin obtained by hardening under the hardening conditions of the above hardening method. The epoxy resin cured product is suitable for use in a semiconductor sealing material. Furthermore, the present invention relates to a semiconductor device characterized by sealing a semiconductor element with the cured epoxy resin.

When the epoxy resin composition of the present invention is heat-cured, it can be an epoxy resin cured product, and the cured product can be excellent in high heat resistance, high-temperature long-term thermal decomposition stability, high fluidity, and the like. Used in electrical. In the use of electronic component seals, circuit substrate materials, etc.

Fig. 1 is a GPC chart of the phenol resin obtained in Synthesis Example 1.

2 is a GPC chart of the epoxy resin obtained in Synthesis Example 2.

Fig. 3 is a GPC chart of the phenol resin obtained in Synthesis Example 3.

4 is a GPC chart of the epoxy resin obtained in Synthesis Example 4.

Fig. 5 is a GPC chart of the phenol resin obtained in Synthesis Example 5.

Fig. 6 is a GPC chart of the epoxy resin obtained in Synthesis Example 6.

Fig. 7 is a GPC chart of the phenol resin obtained in Synthesis Example 7.

Fig. 8 is a GPC chart of the epoxy resin obtained in Synthesis Example 8.

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention can be produced by reacting the polyvalent hydroxy compound represented by the above formula (1) with epichlorohydrin, represented by the above formula (2). Moreover, the polyvalent hydroxy compound can be produced by reacting a phenol with glyoxal.

In the general formulae (1) and (2), the same symbols have the same meaning, and R independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Preferably, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is a repeating number, and usually n is a mixture of different components, but is preferably composed of components of 0 to 10. Further, 10% or more is preferably a polymer having n = 1 or more. The % of n is an area % measured by colloidal permeation chromatography (GPC), and an area % of a polymer component having n of 1 or more is preferably 10% or more.

In the past, the above-mentioned polyhydric hydroxy compound having a 4-functionality of n=0 which is generally produced is a large excess of a phenol compound with respect to glyoxal. Got it. There is no limitation on the amount of the phenol compound to be used in the reaction of the phenol compound with the glyoxal. The amount of the glyoxal used is 0.02 to 0.2 mol, preferably 0.04 to 0.1 mol, relative to the phenol compound. ear. When the amount of glyoxal used is more than 0.2 mol, the softening point of the polyvalent hydroxy compound and the epoxy resin produced therefrom becomes high, which hinders the forming workability, and the formation of n=0 body becomes more than 0.02 mol. And the amount of excess phenol removed after the end of the reaction becomes large, which is industrially unsatisfactory. The area % of the polymer component in which the polyvalent hydroxy compound n of the polymer-containing epoxy resin of the present invention is 1 or more is 10% or more, which can be adjusted by adjusting the phenol compound and the glyoxal The ear ratio becomes the desired polymer content.

Usually, the reaction is in the conventional inorganic acid, organic acid, etc. It is carried out in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid, or zinc chloride, aluminum chloride, iron chloride, and trifluorochloride. A Lewis acid such as boron or a solid acid such as activated clay, ceria-alumina or zeolite.

Usually, the reaction is carried out at 10~250 °C for 1~20 small Time. Further, the solvent for the reaction is preferably used, for example, methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether (diglyme), triethyl ethane. An alcohol such as diol dimethyl ether or an aromatic compound such as benzene, toluene, chlorobenzene or dichlorobenzene. Particularly, from the viewpoint of solubility, ethyl cellosolve, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether are preferred. After the reaction is completed, the obtained polyhydric hydroxy resin may be removed by vacuum distillation, washing with water or reprecipitation in a weak solvent, but may be dissolved. The agent is used directly as a raw material for the epoxidation reaction.

The polyhydroxy compound thus produced is of the above formula (1) In the area % measured by GPC, the component of n = 1 or more is 10% or more, preferably 11% or more, more preferably 12% or more. Further, when the ratio of the polymer is increased, the viscosity of the epoxy resin obtained by the use is increased to lower the moldability. Therefore, the component of n=1 or more is preferably 60% or less, more preferably 50% or less, and most preferably It is 40% or less. Further, the average number of repetitions n (number average) is 0 to 5, but the composition adjusted to n = 1 or more contains 10% or more. Therefore, n is approximately 0.10 or more.

The epoxy resin of the present invention is a polymer represented by the general formula (2) An epoxy resin having a 4-functional epoxy compound having a n=0 component as a main component in the mixture. When a polyvalent hydroxy compound containing 10% or more of n = 1 or more components is used as a raw material, in the epoxidation step, since n is not left, the n is not changed, so it is considered to be the same as the raw material. The content rate. Although the epoxy resin of the present invention contains a polymer component bonded by a methine chain, the principle is not clear, but it is presumed that the crosslinking is relatively dense, and the result is considered to be excellent in thermal decomposition stability. .

That is, in the epoxy resin of the formula (2), n = 0 (4 functional groups) When the proportion of the fraction is increased, the ethylene unit is closest to the phenyl epoxidone unit by 1:4. On the other hand, when a polyvalent hydroxy compound having a higher ratio of n=1 (7-functional) and n=2 (10-functional) components of a higher functional component is used, the ratio is 2:7 and 3:10, and the ratio is The density of the joint is denser, and the hardened material excellent in heat stability can be obtained by relatively small units of the glycidyl ether. Moreover, it is considered that when a polyfunctional component is added, a hardened substance is used in the reaction with the hardener. The crosslink density is increased, and it can also be a cured product having more excellent thermal stability. However, when the component of n=5 or more is added, since the molecular weight is increased, fluidity or moldability tends to be deteriorated. For this reason, the number of n-ranges 0 to 10 includes n=0, and the average (number average) of n is preferably in the range of 0.1 to 4. Since n is substantially inherited from n of the polyvalent hydroxy compound used as a raw material, the adjustment of n is carried out by adjusting n of the polyvalent hydroxy compound.

The epoxy resin of the present invention can be obtained by the above polyhydric hydroxy resin Manufactured by reacting with epichlorohydrin. This reaction can be carried out in the same manner as in the usual epoxidation reaction. For example, after dissolving the polyhydric hydroxy resin in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, at 50 to 150 ° C, preferably 60 to 120 ° C. The method of reacting for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide to be used is 0.8 to 1.2 moles, preferably 0.9 to 1.0 moles, per mole of the hydroxyl group in the polyvalent hydroxy compound. Further, although epichlorohydrin is used in excess with respect to the hydroxyl group in the polyhydric hydroxy resin, it is usually 1.5 to 15 moles, preferably 2 to 8 moles per mole of the hydroxyl group in the polyvalent hydroxy compound. After the completion of the reaction, the excess epichlorohydrin can be distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and the inorganic salt is removed by filtration and washing with water, followed by distilling off the solvent to obtain the formula (2). Indicates the epoxy resin. However, the reaction of the epoxidized propyl group with the unreacted phenolic hydroxyl group also proceeds during the epoxidation reaction, and a polymer which is linked by a propylene group is also formed. Therefore, it is necessary to adjust the reaction conditions to the above range. The polymer of the tetrafunctional epoxy compound is the same, but the heat resistance is largely different depending on the binding site.

In addition, the viscosity and softening point of the epoxy resin can be modified The molar ratio of the phenolic compound to the glyoxal of the polyhydroxy resin in the synthesis of the epoxy resin can be easily adjusted, but the viscosity of the inorganic filler is better at 150 ° C from the viewpoint of high filling of the inorganic filler. It is 3.0Pa. s below, better for 1.0Pa. Below s, it is better to 0.5Pa. s below. Further, the softening point thereof is preferably 130 ° C or lower.

Next, the epoxy resin composition of the present invention is said Bright. The epoxy resin composition of the present invention comprises the above-mentioned epoxy resin, hardener, hardening catalyst and inorganic filler of the present invention. Here, the epoxy resin of the present invention is an epoxy resin obtained by reacting an epoxy resin represented by the formula (2) or a polyvalent hydroxy compound represented by the formula (1) with epichlorohydrin.

The hardener used in the epoxy resin composition is phenol A hardener. In the field of requiring high electrical insulation properties of semiconductor sealing materials and the like, polyphenols are preferably used as the curing agent. Specific examples of the hardener are listed below.

The polyphenols are, for example, bisphenol A, bisphenol F, bisphenol S, Bisphenol, hydroquinone, resorcinol, catechol, biphenols, naphthalenediols, etc. 2 phenols, and ginseng-(4-hydroxyphenyl)methane, 1,1,2 , 2-anthracene (4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthol novolac, dicyclopentadiene phenol resin, phenol aralkyl resin, etc. The above phenols and the like. Further, there are phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, and isophthalic acid. Diphenols such as diphenol, catechol, naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylene glycol, p-xylene glycol dimethyl ether, diethylene Benzobenzene, diisopropenylbenzene, dimethoxy A polyphenolic compound synthesized by a crosslinking reaction of a methylated biphenyl, a divinylbiphenyl or a diisopropenylbiphenyl, and a biphenyl aryl obtained from a phenol or a bischloromethylbiphenyl. An alkyl type phenol resin or the like. Further, examples thereof include naphthol aralkyl resins synthesized from naphthols and p-xylene dichloride, and polyvalent hydroxy compounds represented by the formula (1).

The amount of hardener is determined by considering the epoxy group in the epoxy resin. It is formulated in an equilibrium with the equivalent of the hydroxyl group of the polyhydric phenol. The equivalent ratio of the epoxy resin and the hardener is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0, more preferably in the range of 0.8 to 1.5. When it is larger or smaller, the hardenability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, and the like of the cured product are lowered.

Moreover, the epoxy resin composition may also be formulated with aromatic Other hardeners other than the hydroxy compound are used as the hardener component. The epoxy resin in this case is, for example, a diamine diamine, an acid anhydride, an aromatic or an aliphatic amine. One type of these hardening agents or a mixture of two or more types may be used for the resin composition. However, the amount of the curing agent other than the phenolic curing agent is preferably 50% by weight or less based on the total amount of the curing agent.

Moreover, the epoxy resin composition can also be formulated with a general formula (2) Other epoxy resins other than the epoxy resin shown as the epoxy resin component. As the epoxy resin in this case, all of the general epoxy resins having two or more epoxy groups in the molecule can be used. For example, it is exemplified by bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxyl Epoxides of 2-membered phenols such as benzene, resorcinol and naphthalenediol, ginseng-(4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl)ethane , An epoxide of a phenolic phenolic varnish, an o-cresol novolac, and the like, a epoxide of a diol of three or more phenols, an epoxide of a co-condensation resin obtained from dicyclopentadiene and a phenol, and a cresol, a formaldehyde, and an alkoxy group. a condensed resin epoxide obtained by substituting a naphthalene, an epoxide of a phenol aralkyl resin obtained from a phenol and a p-xylene dichloride, and a phenol and a bischloromethylbiphenyl. An epoxide of a phenylaralkyl type phenol resin, an epoxide of a naphthol aralkyl resin synthesized from naphthols and p-xylene dichloride, and the like. These epoxy resins may be used alone or in combination of two or more. Further, when the epoxy resin of the present invention is used as a constituent of the essential component, the amount of the epoxy resin represented by the formula (2) is preferably from 5 to 100% by weight, preferably from 60 to 100% by weight in the entire epoxy resin. The range of %.

Inorganic fillers are listed as spherical or broken molten dioxins Cerium oxide powder such as bismuth oxide or cerium oxide, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina, boron nitride, aluminum nitride, tantalum nitride, tantalum carbide, Titanium nitride, zinc oxide, tungsten carbide, magnesium oxide, and the like. A preferred blending amount for use in the semiconductor sealing material is 70% by weight or more, more preferably 80% by weight or more.

As a hardening catalyst, it promotes hardening and improves forming For the purpose of fluidity at the time, it is preferred to use a hardening catalyst (high temperature active catalyst) having an active point in a high temperature region in the epoxy resin composition.

The content of the hardening catalyst is 100 parts by weight relative to the epoxy resin It is in the range of 0.2 to 5 parts by weight. It is preferably from 0.5 to 3 parts by weight, more preferably from 0.5 to 2.5 parts by weight. When the value is less than this value, the curability is lowered, and conversely, when it is larger than this, the fluidity improving effect at the time of molding cannot be sufficiently exhibited.

DSC of epoxy resin composition using high temperature active catalyst The exothermic peak temperature is 150 ° C or higher, preferably 155 ° C or higher, more preferably 165 ° C or higher. When the exothermic temperature is lower than 150 ° C, the curing reaction proceeds at the time of molding, and the fluidity improving effect cannot be sufficiently exhibited. The DSC exothermic peak temperature was measured at a temperature rising rate of 10 ° C /min, and the temperature at which the maximum exothermic peak was exhibited when the epoxy resin composition as a high-temperature active catalyst of the curing catalyst was prepared by DSC measurement.

As for the hardening catalyst or high temperature active catalyst, for example, Examples are imidazoles, organophosphines, amines, and the like. The imidazoles are exemplified by 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-heptadecylimidazole, 2,4-diamine. -6-[2'-dimethylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-three Oxazine, etc., organophosphines are exemplified by gins-(2,6-dimethoxyphenyl)phosphine, tri-p-tolylphosphine, ginseng (p-chlorophenyl)phosphine, and para-p-methoxybenzene. The phosphines and the like are exemplified by 1,8-diazabicyclo (5.4.0) undecenene-7 phenol novolac salt and the like. The amount of addition is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

In the present invention, by using a specific active temperature region The high-temperature active catalyst of the domain acts as a hardening catalyst to suppress the decrease of fluidity. Further, regarding the hardening conditions, it is found that the hardening conditions at special high temperatures have a great influence on the glass transition temperature especially when the epoxy resin of the present invention is used. .

The Brazilian resin brown body can be used as needed in the resin composition of the present invention. Release agent such as carnauba wax, OP wax, coupling agent such as 4-aminopropyl ethoxy decane, γ-glycidoxypropyltrimethoxy decane, coloring agent such as carbon black, and trioxide A flame retardant such as ruthenium or a slip agent such as calcium stearate.

The epoxy resin composition of the present invention can also be appropriately formulated and polymerized. Ester, polyamide, polyimine, polyether, polyurethane, petroleum resin, enamel resin, hydrazine. An oligo or a polymer compound of a coumarin-filled resin or a phenoxy resin is used as another modifier. The amount of addition is usually in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

In addition, the epoxy resin composition of the invention can be adjusted Additives such as materials, flame retardants, shake imparting agents, coupling agents, fluidity enhancers, and antioxidants.

As for the pigment, there are organic or inorganic body pigments, Flaky pigments, etc. Examples of the shake imparting agent include an anthraquinone-based, a castor oil-based, an aliphatic guanamine wax, an oxidized polyethylene wax, and an organic bentonite-based.

The epoxy resin composition of the present invention can be dissolved in an organic solvent After being in a paint state, it is impregnated into a fibrous material such as a glass cloth, an linoleamide nonwoven fabric, or a liquid crystal polymer such as a polyester nonwoven fabric, and then removed by a solvent to obtain a prepreg. Further, it may be applied to a sheet of a copper foil, a stainless steel foil, a polyimide film, a polyester film or the like as a laminate as the case may be.

The preparation method of the epoxy resin composition of the present invention is Any method can be used to uniformly disperse and mix the various raw materials. As a general method, a material which is sufficiently mixed with a specific blending amount by a kneading machine or the like is melt-kneaded by a mixing roll or an extruder, and is cooled and pulverized.

The epoxy resin composition of the present invention and the hardened material thereof are particularly suitable Used as a seal for semiconductor devices.

The cured product of the present invention can be composed of the above epoxy resin The material is hardened by heat. In order to obtain a cured product using the epoxy resin composition of the present invention, methods such as transfer molding, press molding, injection molding, injection molding, extrusion molding, and the like can be applied, but in terms of mass productivity, Mold forming is preferred.

The hardening method of the epoxy resin composition of the present invention is 100 °C~200°C, preferably 120°C~190°C, better after forming at 150~180°C, after 200°C~300°C, preferably 220°C~280°C, better after 230~270°C By manufacturing, it is possible to obtain a cured product excellent in heat resistance, high-temperature long-term thermal decomposition stability, and high fluidity.

The forming time is preferably from 1 to 60 minutes, more preferably from 1 minute to 10 minutes. When the forming time is long, the productivity is deteriorated, and when it is too short, it is difficult to demold. The post-hardening time is preferably from 10 minutes to 10 hours, more preferably from 30 minutes to 8 hours, and most preferably from 2 hours to 6 hours. When the post-hardening time is short, the hardening cannot be sufficiently performed, and sufficient characteristics such as heat resistance and mechanical properties cannot be obtained. Moreover, productivity is lowered over 10 hours.

The epoxy resin composition of the present invention is even in general epoxy trees When the fat composition is not able to react, the hardening reaction can be carried out in the hardening temperature region, and a cured product having extremely high heat resistance, thermal decomposition resistance, mechanical properties, and the like can be obtained.

[Examples]

The following is specifically described based on synthesis examples, examples, and comparative examples. this invention.

Synthesis Example 1

3,500 g (37.2 mol) of phenol and 2.36 g of p-toluenesulfonic acid as an acid catalyst were fed into a 5 L four-necked flask, and the temperature was raised to 50 °C. Next, 360 g of a 40% aqueous solution of glyoxal was added dropwise thereto over 30 minutes while stirring at 50 ° C, and after the completion of the dropwise addition, the mixture was reacted at 50 ° C for 30 minutes, and reacted at 100 ° C for 2 hours. Subsequently, the mixture was dehydrated at 100 ° C under reduced pressure, and then reacted at 100 ° C for 4 hours. After completion of the reaction, phenol was distilled off to obtain 711 g of a phenol resin. The hydroxyl equivalent of the obtained resin was 119.4 g/eq. Further, as a result of GPC measurement, the component of n=0: 71.5%, and the component of n=1 or more: 13.2%.

Synthesis Example 2

500 g of the phenol resin obtained in Synthesis Example 1, 377 g of diethylene glycol dimethyl ether, and 2511 g of epichlorohydrin were fed into a 5 L four-necked flask, and the temperature was raised to 60 °C. Next, 48.2 g of a 49% potassium hydroxide aqueous solution was added dropwise thereto over 2 hours to carry out a preliminary reaction, and then 298.9 g of a 49% aqueous sodium hydroxide solution was added dropwise thereto at 63 ° C for 3.5 hours under reduced pressure, and the droplet was separated by a separation tank. The water distilled off under reflux is added to epichlorohydrin and the epichlorohydrin is returned to the reaction vessel, and the water is discharged outside the system for reaction. After completion of the reaction, the resulting salt was removed by filtration, and then washed with water, and then epichlorohydrin was distilled off to obtain 660 g of epoxy resin (epoxy resin A). The epoxy equivalent of the obtained resin was 182.0 g/eq., and the melt viscosity at 150 ° C was 0.35 Pa. s.

Synthesis Example 3

Into a 3 L four-necked flask, 1000 g of phenol, 232 g of a 40% by weight aqueous solution of glyoxal, and 125 g of acetone were fed, and 187.5 g of 95% by weight of sulfuric acid was added dropwise over 2 hours. Subsequently, the reaction was carried out at 40 ° C for 12 hours, and after completion of the reaction, it was cooled to 15 ° C for neutralization. Next, 632 g of acetone was added, and the precipitate was filtered. Subsequently, the mixture was washed with a mixture of acetone and water, and 1400 g of methanol was fed thereto, and the mixture was heated and refluxed for about 1 hour to dissolve, and then the neutralized salt was removed by filtration while being heated. On the other hand, after the obtained methanol solution was added with 564 g of water under stirring, methanol was distilled off under reduced pressure. Subsequently, after stirring overnight at 15 ° C, it was separated by filtration, and dried under reduced pressure at about 130 ° C to obtain 227 g of a white crystal of phenol. The hydroxyl equivalent of the obtained resin was 103.8 g/eq. Further, as a result of GPC measurement, it was n=0 component: 100%.

Synthesis Example 4

500 g of the phenol resin obtained in Synthesis Example 3, 434 g of diethylene glycol dimethyl ether, and 2896 g of epichlorohydrin were fed into a 5 L four-necked flask, and the temperature was raised to 60 °C. Next, 55.5 g of a 49% potassium hydroxide aqueous solution was added dropwise for 2 hours to carry out a preliminary reaction, and then 344.6 g of a 49% aqueous sodium hydroxide solution was added dropwise at 63 ° C for 3.5 hours under reduced pressure, and the dropwise addition was separated by a separation tank. The distilled water is refluxed with epichlorohydrin and the epichlorohydrin is returned to the reaction vessel, and the water is discharged outside the system for reaction. After completion of the reaction, the salt formed was removed by filtration, and then washed with water to distill off epichlorohydrin to obtain 693 g of an epoxy resin (epoxy resin B). The obtained resin had an epoxy equivalent of 173.0 g/eq., which was confirmed to be a crystalline resin having a melting point of 181 ° C by DSC.

Synthesis Example 5

3,500 g (37.2 mol) of phenol and 1.77 g of p-toluenesulfonic acid as an acid catalyst were fed into a 5 L four-necked flask, and the temperature was raised to 50 °C. Next, 270 g of a 40% aqueous solution of glyoxal was added dropwise thereto over 30 minutes while stirring at 50 ° C, and after the completion of the dropwise addition, the reaction was carried out at 50 ° C for 1 hour, and at 60 ° C for 2.5 hours. Subsequently, the mixture was dehydrated at 60 ° C under reduced pressure, and then reacted at 60 ° C for 8.5 hours. After completion of the reaction, phenol was distilled off to obtain 534 g of a phenol resin. The hydroxyl equivalent of the obtained resin was 112.0 g/eq. Further, as a result of GPC measurement, the component of n = 0: 79.3%, and the component of n = 1 or more: 8.6%.

Synthesis Example 6

500 g of the phenol resin obtained in Synthesis Example 5, 403 g of diethylene glycol dimethyl ether, and 2684 g of epichlorohydrin were fed into a 5 L four-necked flask, and the temperature was raised to 60 °C. Next, 51.5 g of a 49% potassium hydroxide aqueous solution was added dropwise thereto over 2 hours to carry out a preliminary reaction, and then 315.3 g of a 49% aqueous sodium hydroxide solution was added dropwise thereto at 63 ° C for 3.5 hours under reduced pressure to separate the dropwise addition in a separation tank. The distilled water and epichlorohydrin are refluxed to return epichlorohydrin to the reaction vessel, and the water is discharged outside the system for reaction. After completion of the reaction, the salt formed was removed by filtration, and epichlorohydrin was distilled off by water to obtain 675 g of epoxy resin (epoxy resin D). The epoxy equivalent of the obtained resin was 179.5 g/eq. The melt viscosity at 150 ° C is 0.28 Pa. s.

Synthesis Example 7

Into a 5 L four-necked flask, 300 g (3.2 mol) of phenol and 1.01 g of p-toluenesulfonic acid as an acid catalyst were fed, and the temperature was raised to 50 °C. Next, 154 g of a 40% aqueous solution of glyoxal was added dropwise thereto over 30 minutes while stirring at 50 ° C, and after the completion of the dropwise addition, the reaction was carried out at 50 ° C for 30 minutes, and at 100 ° C for 2 hours. Subsequently, the mixture was dehydrated at 100 ° C under reduced pressure, and then reacted at 100 ° C for 4 hours. After completion of the reaction, phenol was distilled off to obtain 226 g of a phenol resin. The hydroxyl equivalent of the obtained resin was 130.6 g/eq. Further, as a result of GPC measurement, the component of n = 0: 29.9%, and the component of n = 1 or more: 55.3%.

Synthesis Example 8

125 g of the phenol resin obtained in Synthesis Example 7, 86 g of diethylene glycol dimethyl ether, and 575 g of epichlorohydrin were fed into a 5 L four-necked flask, and the temperature was raised to 60 °C. Next, 11.0 g of a 49% potassium hydroxide aqueous solution was added dropwise thereto over 2 hours to carry out a preliminary reaction, and then 67.5 g of a 49% aqueous sodium hydroxide solution was added dropwise thereto at 63 ° C for 3.5 hours under reduced pressure, and the dropwise addition was separated by a separation tank. The distilled water is refluxed with epichlorohydrin and the epichlorohydrin is returned to the reaction vessel, and the water is discharged outside the system for reaction. After completion of the reaction, the resulting salt was removed by filtration, and after washing with water, epichlorohydrin was distilled off to obtain 70 g of epoxy resin (epoxy resin E). The epoxy equivalent of the obtained resin was 209.6 g/eq. The melt viscosity at 150 ° C is 3.08 Pa. s.

The GPC patterns of the phenol resins obtained in Synthesis Examples 1, 3, 5, and 7 are shown in Figs. 1, 3, 5, and 7, and the GPC patterns of the epoxy resins obtained in Synthesis Examples 2, 4, 6, and 8 are shown in Fig. 2. , 4, 6, and 8.

Example 1

100 g of the epoxy resin A obtained in Synthesis Example 2 was used as an epoxy resin component, and a phenol novolak (PSM-4324 (manufactured by Kyoei Chemical Industry Co., Ltd.), OH equivalent 105, softening point: 100 ° C) 57.5 g was used as the hardening. Ingredients. Further, 0.7 g of a curing accelerator A and 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were used, and an epoxy resin composition was obtained by kneading. Using the epoxy resin composition, a cured test piece was obtained under the conditions of a molding temperature of 175 ° C, 3 minutes, a post-hardening temperature of 250 ° C, and 5 hours (forming condition A), and then a 5% weight loss temperature was measured. The results are shown in Table 1.

Example 2

A 5% weight loss temperature was measured in the same manner as in Example 1 except that 100 g of the epoxy resin E obtained in Synthesis Example 8 was used as the epoxy resin component. The results are shown in Table 1.

Comparative example 1

A 5% weight loss temperature was measured in the same manner as in Example 1 except that 100 g of the epoxy resin B obtained in Synthesis Example 4 was used as the epoxy resin component. The results are shown in Table 1.

Comparative example 2

A 5% weight loss temperature was measured in the same manner as in Example 1 except that 100 g of the epoxy resin D obtained in Synthesis Example 6 was used as the epoxy resin component. The results are shown in Table 1.

Examples 3 to 15, Comparative Examples 3 and 4

The epoxy resin A, E, or epoxy resin C, hardener, inorganic filler, hardening accelerator (hardening catalyst) and other additives obtained in the above synthesis examples are mixed and blended in the proportions shown in Tables 2 to 3. Epoxy resin composition. The values in the table indicate the parts by weight.

Abbreviation in the table

Epoxy resin C: o-cresol novolac type epoxy resin (epoxy equivalent 200, softening point 65 ° C. manufactured by Nippon Steel Chemical Co., Ltd.)

(hardener)

PN: phenol novolac (PSM-4324, OH equivalent 105, softening point: 100 ° C, manufactured by Qun Rong Chemical Industry Co., Ltd.)

TPM: trisphenol methane (TPM-100, OH equivalent 97.5, softening point 105 ° C, manufactured by Qun Rong Chemical Industry Co., Ltd.)

(inorganic filler)

Spherical dioxide system (FB-8S, manufactured by Electric Chemical Industry Co., Ltd.)

(hardening accelerator)

A: 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

B: 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ-PW, manufactured by Shikoku Chemicals Co., Ltd.)

C: ginseng-(2,6-dimethoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(decane coupling agent)

4-aminopropyl ethoxy decane (KBR-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

(release agent)

Carnauba wax (TOWAX 171, manufactured by East Asia Chemical Co., Ltd.)

(Colorant)

Carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation)

Using this epoxy resin composition, it was shaped by the molding conditions shown below. After obtaining a cured test piece, it was used for various physical properties. The results are shown in Tables 2 to 3.

Forming conditions

A: forming temperature 175 ° C, 3 minutes, post-hardening temperature 250 ° C, 5 hours

B: forming temperature 175 ° C, 3 minutes, post-hardening temperature 175 ° C, 5 hours

1) Determination of epoxy equivalent

Using a potentiometric titration apparatus, methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and the mixture was measured by a potentiometric titration apparatus using a 0.1 mol/L perchloric acid-acetic acid solution.

2) Melt viscosity

The measurement was carried out at 150 ° C using a CV-1S cone-plate viscometer manufactured by East Asia Industrial Co., Ltd.

3) Glass transfer point (Tg)

The Tg was determined under the conditions of a temperature increase rate of 10 ° C /min using a TMAKO instrument type TMA6100 thermomechanical measuring device.

4) Long-term thermal decomposition stability evaluation (weight retention rate)

The weight retention ratio (wt%) was determined from the difference between the weight of the test piece after 1000 hours at 250 ° C and the weight of the test piece before heating using a rotary frame thermostat (GPHH-201, manufactured by TABAI ESPEC Co., Ltd.).

5) Spiral flow

According to the specification (EMMI-1-66), the epoxy resin composition was molded by a spiral flow measurement mold under the conditions of a spiral flow injection pressure (150 Kgf/cm ² ) and a curing time of 3 minutes, and the temperature was investigated at 170 ° C. The length of the flow.

6) DSC heating peak temperature

The exothermic peak temperature was determined by a DSC6200 type thermomechanical measuring apparatus manufactured by SEIKO Instruments at a temperature rising rate of 10 ° C /min.

7) 5% weight reduction temperature

Using a TG/DTA 6200 type thermomechanical measuring apparatus manufactured by SEIKO Instruments, a 5% weight reduction temperature was obtained under a nitrogen atmosphere at a temperature increase rate of 10 ° C /min.

8) Bending strength and bending flexibility

According to JIS K 6911, the 3-point bending test method is used at normal temperature and 250 ° C. The measurement was carried out.

9) Flexural strength. Elasticity retention rate

The bending strength and the bending elastic modulus at a high temperature (250 ° C) were obtained with respect to the bending strength and the bending elastic modulus at normal temperature. The higher the value, the less the change in physical properties with room temperature.

Claims (10)

An epoxy resin represented by the following formula (2), Here, R independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group, and n is a repeating number, and 10% or more of n is a polymer of 1 or more. An epoxy resin characterized by being reacted with epichlorohydrin by a polyhydric hydroxy compound having a composition of % by weight or more and having a component of n = 1 or more as measured by colloidal permeation chromatography. And got it, Here, R independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, G represents a glycidyl group, and n represents a repeating number. An epoxy resin composition comprising the epoxy resin according to claim 2, a phenolic curing agent, a curing catalyst, and an inorganic filler. An epoxy resin composition comprising the epoxy resin according to claim 1, a phenolic curing agent, a curing catalyst, and an inorganic filler. The epoxy resin composition of claim 3, wherein the hardening catalyst is at least one selected from the group consisting of imidazoles, organophosphines, and amines. The epoxy resin composition according to claim 3, wherein the curing catalyst is an epoxy resin composition measured at a temperature rising rate of 10 ° C /min by DSC, and the peak of the heat generation peak is 150 ° C or higher. A method for curing an epoxy resin composition, characterized in that after the epoxy resin composition of claim 3 is formed at 100 ° C to 200 ° C, post-curing is carried out at 200 ° C to 300 ° C. An epoxy resin cured product obtained by forming an epoxy resin composition according to claim 3 at 100 ° C to 200 ° C and then post-hardening at 200 ° C to 300 ° C. The cured epoxy resin of claim 8 which is an epoxy resin cured product for a semiconductor sealing material. A semiconductor device characterized by sealing a semiconductor element with an epoxy resin cured material as claimed in claim 9.