TWI522385B - An epoxy resin, an epoxy resin composition, and a cured product thereof - Google Patents

Description

Epoxy resin, epoxy resin composition, and cured product thereof

The present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof which are provided with a cured product excellent in heat resistance and water resistance.

The epoxy resin composition is widely used in electrical/electronic parts, structural materials, adhesives, paints, and the like due to workability and excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance) of the cured product. in.

However, in recent years, in the field of electric/electronics, with the development of the resin composition, high purity, moisture resistance, adhesion, dielectric properties, and high filling of fillers (inorganic or organic fillers) are required. Various characteristics such as low viscosity and improved reactivity for shortening the molding cycle are further improved. Further, as a structural material, materials which are lightweight and excellent in mechanical properties such as aerospace materials and entertainment/exercise equipment applications are required. In particular, in the field of semiconductor sealing and the substrate (substrate itself or its peripheral materials), the required characteristics are increasing year by year, and for example, high Tg of the peripheral material caused by an increase in the driving temperature of the semiconductor is required.

In general, when the epoxy resin is high in Tg, the water absorption rate is increased (Non-Patent Document 1). This is the effect of increased crosslink density. However, in the case of requiring high Tg for semiconductor peripheral materials requiring low moisture absorption, development of resins having such opposite characteristics is an urgent task.

Further, similarly, when the Tg is high, the electrical reliability tends to decrease. That is, the dielectric constant and the dielectric loss tangent deteriorate. In the development of the use of electrical and electronic materials, it is necessary to maintain high electrical reliability. Tg reduces the dielectric constant and dielectric loss tangent.

Non-Patent Document 1: Kojiro Ichiro, "Relationship between Chemical Structure and Properties of Epoxy Resin", DIC Technical Review No. 7, Japan, 2001, p. 7

The present invention has produced research results in order to solve such a problem, and provides an epoxy resin whose cured product is highly heat-resistant and has a low water absorption property and a low dielectric constant.

The inventors of the present invention have diligently studied to solve the above problems, and as a result, have completed the present invention.

That is, the present invention provides: (1) an epoxy resin obtained by glycidylating a naphthol-cresol novolac type phenol resin, wherein the naphthol-cresol novolak type phenol resin is The naphthol is reacted with cresol and an aldehyde, and the ratio of the naphthol to the naphthol in the naphthol is 1 to 10% by weight when the naphthol is reacted with the aldehyde; (2) the epoxy resin of (1), wherein The naphthol-cresol novolac type phenol resin described in (1), the naphthol and cresol reacted with aldehyde and the weight ratio of naphthol to cresol is 65:35 to 85:15, and the obtained naphthol - cresol novolak type phenolic resin softening point is 100 ° C ~ 150 ° C; (3) such as (1) or (2) epoxy resin, in ¹³ C-NMR, 74 ~ 76 ppm peak The total area and the peak area of 68~71 ppm are 60:40~80:20, and the softening point is 85°C~100°C; (4) The ring of any one of (1) to (3) An oxy-resin having a (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.4 to 2.5; (5) an epoxy resin composition containing the epoxy resin of any of (1) to (4) and hardening a curing agent; (6) a hardened material which is hardened by the epoxy resin composition of (5) .

The epoxy resin composition using the epoxy resin of the present invention provides a cured product which can simultaneously achieve heat resistance and water resistance, and an insulating material for electrical and electronic parts and a laminate (printed circuit board, build-up substrate, etc.) or CFRP. Various composite materials such as carbon fiber reinforced plastics, adhesives, and coatings are useful. In particular, it is extremely useful for protecting a semiconductor sealing material or a laminate material for a semiconductor element.

The epoxy resin of the present invention is obtained by glycidylating a naphthol-cresol novolac type phenol resin, and the naphthol-cresol novolac type phenol resin is reacted with naphthol and cresol with an aldehyde. Further, when the naphthol and the cresol are reacted with the aldehyde, the ratio of the α-naphthol in the naphthol is 1 to 10% by weight.

A naphthol-cresol novolak type phenolic resin obtained by reacting naphthol with cresol and aldehyde, and reacting naphthol with cresol and aldehyde, wherein the ratio of α-naphthol in the naphthol is 1 to 10% by weight ( NCN) is not particularly limited, and is, for example, represented by the following formula (1): [Chemical 1]

(wherein, n represents the average number of repeats. Further, Ar and R in the plural exist independently, R represents a methyl group or a hydrogen atom, and Ar represents 1-naphthol, 2-naphthol, cresol as shown above ).

NCN is usually obtained by reacting naphthol, cresol with formaldehyde (or its equivalent) under acidic or basic conditions.

Specifically, naphthol, cresol, and formaldehyde (or an equivalent thereof) and a catalyst may be added simultaneously or sequentially, and the reaction is usually carried out at 0 to 150 ° C, preferably 10 to 130 ° C. Here, the naphthol may be preferentially reacted by carrying out the reaction at a low temperature.

In this case, when it is 0 ° C or more, the progress of the reaction does not become slow, and it does not take a long time and is excellent in productivity, and is preferable. Further, when the temperature is 150 ° C or lower, the reaction does not proceed once, and the naphthol which does not participate in the reaction does not increase, which is preferable. By reacting naphthol relatively preferentially by carrying out the reaction in the above range, a compound having a small residual amount of naphthol can be obtained.

Furthermore, the reaction time is usually 5 to 150 hours.

The NCN obtained in the above manner may also be used without purification depending on the use. However, in general, after the completion of the reaction, the reaction mixture is neutralized, and then the unreacted raw materials and the solvent are removed under heating and reduced pressure, thereby being purified and used. Further, in the neutralization step, various salts such as alkalis and phosphates, buffers, and the like may be added, and water washing or the like may be added. However, it is more convenient and effective to use both. In the case where the reaction does not sufficiently consume naphthol, the residual amount of naphthol is preferably 1% or less by foaming of an inert gas such as thin film distillation or nitrogen.

Examples of the solvent which can be used in the synthesis of NCN include methanol, ethanol, propanol, isopropanol, toluene, xylene, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc., but are not limited thereto. These may be used alone or in combination of two or more. In the case of using a solvent, the amount thereof is usually from 5 to 500 parts by weight, preferably from 10 to 300 parts by weight, per 100 parts by weight of the total amount of naphthol and cresol.

As the catalyst, any catalyst which is acidic or alkaline can be used.

Specific examples of the acidic catalyst that can be used include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid, and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acid, and tetrachlorinated. Other organic or inorganic acid salts which exhibit acidity such as tin, zinc chloride or ferric chloride are generally used for an acidic catalyst for the production of a novolak resin.

Specific examples of the basic catalyst that can be used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; and sodium methoxide ( Sodium methoxide), alkali metal alkoxide such as sodium ethoxide, potassium methoxide, potassium ethoxide or potassium t-butoxide; alkaline earth metal alkoxide such as magnesium methoxide or magnesium ethoxide.

Further, an amine-based catalyst may be used, and examples thereof include triethylamine, ethanolamine, pyridine, piperidine, and morpholine. In particular, when an amine-based catalyst is used, it can also be used as a solvent.

These catalysts are not limited to those listed above, and may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.005 to 2.0 times moles, preferably 0.01 to 1.1 times the molar amount, relative to the total amount of naphthol and cresol. Further, when the catalyst is used as a solvent, it is preferably added in an amount of about 30 to 200% by weight based on the total amount of naphthol and cresol.

As described above, the naphthol-cresol novolac type phenol-based resin obtained by reacting naphthol, cresol and formaldehyde is obtained by random polymerization, and thus the naphthalene skeleton and the phenol skeleton are randomly arranged.

In the present invention, as the naphthol, β-naphthol and α-naphthol can be used in combination, and as the cresol, o-cresol, m-cresol, p-cresol or a mixture of two or more kinds thereof can be used.

Here, in the naphthol used in the reaction, the ratio of α-naphthol is 1 to 10% by weight.

The weight ratio of naphthol to cresol used in the reaction is preferably from 65:35 to 85:15, more preferably from 62:38 to 80:20, and particularly preferably from 62:38 to 76:24. On the other hand, a preferred ratio of high heat resistance and low water absorption is 71:29 to 85:15. When the amount of the naphthol is 62% by weight or more, the target high heat resistance and low moisture absorption characteristics are likely to occur, and when the amount of the naphthol is 85% by weight or less, the control of the reaction is easy, and the residual naphthol is reduced. Preferably. The naphthol residue is poor in terms of odor, toxicity, and heat resistance of the cured product.

Further, in the present invention, when naphthol and cresol are reacted with an aldehyde, naphthol The ratio of β-naphthol to α-naphthol is from 1 to 10% by weight based on the total amount of naphthol. When the α-naphthol is less than 1% by weight, the heat resistance does not increase, and if the α-naphthol exceeds 10% by weight, the control of the reaction is difficult, and the amount of the residual naphthol increases. Further, there is a method of controlling the molecular weight to reduce residual naphthol by condensation after methylolation of naphthol or cresol, but it is not only complicated to manufacture but also poor in productivity and less distributed, and less distributed. Therefore, heat resistance is insufficient.

Further, the NCN at this time preferably has a softening point of 100 to 150 °C. The skeleton is characterized by its molecular weight, and if it is related to a molecule having a softening point of 100 ° C or more, the target heat resistance is likely to occur. Moreover, when the softening point is 150 ° C or less, handling is easy, and it is easy to reduce residual naphthol, which is preferable. Furthermore, the residue of naphthol is not safe for the user. In the present invention, it is important to be at least 1% or less.

The epoxy resin of the present invention is obtained by glycidylating the above NCN.

In order to glycidylate the above NCN, it is preferred to react the above NCN with an epihalohydrin.

Examples of the epihalohydrin used in the reaction of NCN with epihalohydrin include epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, etc., and industrially preferred in the present invention. Epichlorohydrin readily available. The amount of epihalohydrin used is usually from 3.0 to 10 moles, preferably from 3.5 to 8 moles, per mole of hydroxyl group of NCN.

In the above epoxidation reaction, an alkali metal hydroxide is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and the like. Further, the alkali metal hydroxide may be used in the form of a solid or may be used in the form of an aqueous solution. For example, when the alkali metal hydroxide is used in the form of an aqueous solution, the epoxidation reaction can be carried out by continuously adding an aqueous solution of an alkali metal hydroxide to the reaction system and decompressing it. The water and the epihalohydrin are continuously distilled off under normal pressure or under normal pressure, and the liquid is separated to remove water, and the epihalohydrin is continuously returned to the reaction system. Further, in the case of using a solid, it is preferable to use a sheet in terms of problems such as ease of handling and solubility. The amount of the alkali metal hydroxide used is usually from 0.90 to 1.5 moles, preferably from 0.95 to 1.25 moles, more preferably from 0.99 to 1.15 moles, relative to the hydroxyl group of the NCN.

In the above epoxidation reaction, in order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is preferably added as a catalyst. The quaternary ammonium salt is used in an amount of usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of NCN.

In the epoxidation reaction, an alcohol such as methanol, ethanol or isopropyl alcohol; an aprotic polar solvent such as dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran or dioxane is added to carry out the reaction on the reaction. Preferably.

In the case of using the above alcohols, the amount thereof to be used is usually 2 to 50% by mass, preferably 4 to 20% by mass based on the amount of the epihalohydrin used. On the other hand, in the case of using the above aprotic polar solvent, the amount thereof to be used is usually 5 to 100% by mass, preferably 10 to 80% by mass based on the amount of the epihalohydrin used.

In the above epoxidation reaction, the reaction temperature is usually from 30 to 90 ° C, preferably from 35 to 80 ° C. On the other hand, the reaction time is usually 0.5 to 10 hours. It is preferably 1 to 8 hours. The reactants of the epoxidation reaction can be purified by washing with water or without washing with water and removing epihalohydrin or a solvent under heating and reduced pressure. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the recovered reactant may be dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydrogen such as sodium hydroxide or potassium hydroxide may be added. The ring solution of the by-product is carried out by the aqueous solution of the oxide, so that the by-product, the halo alcohol, is surely closed.

In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of NCN used in the epoxidation. Further, the reaction temperature is usually from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.

In the epoxidation reaction, after the completion of the reaction, the salt formed is removed by filtration, washing with water, or the like, and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

The epoxy resin obtained in the above manner preferably satisfies the following conditions. The softening point is preferably from 80 to 100 ° C, more preferably from 85 to 100 ° C, and particularly preferably from 85 to 97 ° C. In order to obtain a preferred softening point, it can be adjusted according to the weight ratio of naphthol, cresol or formalin (or its synthetic equivalent) used in the reaction, and naphthol and cresol can be achieved by using the above preferred range. The amount of formalin can be obtained by adding 0.5 to 1.1 moles, more preferably 0.60 to 1.1 moles per 1 equivalent of the phenolic hydroxyl group. Furthermore, formalin can be added at one time or in batches.

Further, the epoxy equivalent is preferably from 200 to 300 g/eq., more preferably from 210 g/eq. to 260 g/eq. The epoxy equivalent is adjusted by the amount of the epihalohydrin used in the reaction, the amount of the naphthol of the raw material, the amount of the cresol, and the molecular weight. The epoxy resin of the present invention having a preferred epoxy equivalent can be used by using the epoxy resin. Softening point Obtained by the same method as described in the adjustment, the amount of epihalohydrin can be obtained by using the above preferred amount.

Further, in the ¹³ C-NMR, the total area of the peaks of 74 to 76 ppm and the total of the peaks of 68 to 71 ppm are preferably 60:40 to 80:20. The peaks of 74 to 76 ppm and 68 to 71 ppm correspond to the peaks of the methylene moiety bonded to the oxirane structure of the glycidyl group bonded to naphthol and cresol.

Further, the average molecular weight of the epoxy resin of the present invention preferably satisfies the following conditions.

The number average molecular weight is preferably from 500 to 1,000, more preferably from 500 to 800. Further, the weight average molecular weight is preferably from 600 to 2,000, more preferably from 600 to 1,700. The epoxy resin of the present invention having a preferred average molecular weight can be adjusted by the weight ratio of naphthol, cresol, or formalin (or its synthetic equivalent) used in the reaction, if formalin is compared to naphthol, When the amount of cresol is small, the molecular weight can be increased, and the smaller the epihalohydrin, the larger the molecular weight.

If the molecular weight is too small, heat resistance does not occur. If the molecular weight is too large, the viscosity is too high, the operation is difficult, and the solubility in a solvent is insufficient, which is not preferable.

Further, the molecular weight distribution in the present invention is important. When the molecular weight distribution is too narrow, sufficient heat resistance and reduction in water absorption cannot be expected. In this case, the heat resistance due to the crosslinking density at the time of crosslinking in the thermosetting stage is improved, and the hydroxyl group is generated during crosslinking to affect the increase in water absorption. In the present invention, not only heat resistance but also a decrease in water absorption rate can be achieved by increasing the number of bonds on the methylene chain in the matrix of the matrix.

The specific molecular weight distribution is preferably (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.4 or more. Further, when the molecular weight distribution is too large, problems such as an excessively high viscosity are generated. Therefore, the maximum value is preferably 2.5.

The molecular weight distribution can be adjusted by the weight ratio of naphthol, cresol, formalin (or its synthetic equivalent) and the amount of epihalohydrin used in the reaction. Specifically, the more the naphthol ratio is, the more easily the molecular weight distribution is narrowed, and the molecular weight distribution can be made narrower by adding fumarin in portions. Further, the molecular weight distribution can be broadened by reducing the amount of epihalohydrin, and the molecular weight distribution can be narrowed by increasing the amount of epihalohydrin. Further, when NCN is produced, the methylene bond is first cut at 80 to 150 ° C and the re-alignment reaction is carried out by re-bonding, whereby the molecular weight distribution can be made wider. Further, in the rearrangement, it is preferred to add 0.005 to 0.1 equivalent of formalin (or a synthetic equivalent thereof) per one equivalent of the phenolic hydroxyl group.

Next, the epoxy resin composition of the present invention will be described.

In the epoxy resin composition of the present invention, the proportion of the epoxy resin of the present invention in all the epoxy resins is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

Examples of the other epoxy resin include a novolac type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, and a phenol aralkyl type epoxy resin.

Specific examples of the other epoxy resin which can be used together with the epoxy resin of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl substituted phenol, aromatic Substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, a polycondensate of an alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzenedialdehyde, crotonaldehyde, cinnamaldehyde, etc.; the above phenols and various diene compounds (dicyclopentadiene, anthracene) Alkene, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, iso a polymer of pentadiene or the like; a polycondensate of the above phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); the above phenols and aromatics a polycondensate of a dimer methanol (benzene dimethanol, biphenyl dimethanol, etc.); the above phenols and an aromatic dichloromethyl group (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) a polycondensate; a polycondensate of the above phenols and an aromatic bisalkoxymethyl group (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) A glycidyl ether epoxy resin, an alicyclic epoxy resin, a glycidylamine epoxy resin, or a glycidyl ester ring obtained by glycidylating the bisphenols and various aldehyde polycondensates or alcohols The oxygen resin or the like is not limited to these as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.

Examples of the curing agent contained in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound, and a carboxylic acid compound. Specific examples of the hardener which can be used include amines such as diaminodiphenylmethane, di-extension ethyltriamine, tri-ethylidenetetramine, diaminodiphenylphosphonium and isophorone diamine. a compound; a polyamine resin synthesized from a dimer of dicyandiamide and linoleic acid and ethylenediamine; Amine compound; phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl acid anhydride, six An acid anhydride compound such as hydrogen phthalic anhydride or methyl hexahydro phthalic anhydride; bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-biphenol, 2, 2 '-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalene Naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane or phenols (phenol, alkyl-substituted phenol, naphthol, Alkyla substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, furfural a polycondensate, a novolac resin, or a reaction of phenol or cresol with a phenyldihydroxymethyl, dimethoxymethyl or halogenated methyl group, or phenol or cresol with bischloromethylbiphenyl a reaction of bismethoxymethylbiphenyl or bishydroxymethylbiphenyl, or phenol and benzene a phenol aralkyl resin which is a reaction product of isopropyl alcohol, benzodiazepine dimethyl ether or benzobis(chloroisopropane) and such a modified substance, or a halogenated bisphenol such as tetrabromobisphenol A, or hydrazine A phenolic compound such as a condensate of an alkene and a phenol; an imidazole, a boron trifluoride-amine complex, a guanidine derivative, or the like, but is not limited thereto. These may be used alone or in combination of two or more.

In the present invention, in terms of heat resistance, chemical resistance, and electrical reliability, a phenol-based compound is preferably used as a curing agent, and particularly in terms of flame retardancy, a novolak resin is preferable. A phenol novolak resin or a cresol novolak resin or a phenol aralkyl resin is preferred. Further, in the present invention, it is preferred to use a curing agent having a softening point of 50 to 100 °C. Softening Point The lower one has a tendency to improve fluidity and flame retardancy, but in terms of improving heat resistance, it is preferred to use a higher softening point.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably from 0.8 to 1.1 equivalents per equivalent of the epoxy group of the epoxy resin. When it is 0.8 equivalent or more or 1.1 equivalent or less with respect to 1 equivalent of an epoxy group, it is hardened completely, and it is preferable to obtain favorable hardening physical property. Further, in the present invention, as a preferable combination of the epoxy resin and the curing agent, the epoxy resin having a softening point of 45 to 70 ° C (more preferably 50 to 65 ° C) and a softening point of 50 to 100 ° C (preferably 55) ~85 ° C) hardener. A resin composition having characteristics of balance in fluidity, flame retardancy, and heat resistance is formed.

The epoxy resin composition of the present invention may further contain a curing accelerator. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl) a tertiary amine such as phenol or 1,8-diaza-bicyclo(5,4,0)undecene-7; a phosphine such as triphenylphosphine; or a metal compound such as stannous octoate. The hardening accelerator is used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, as needed.

The epoxy resin composition of the present invention may further contain a phosphorus-containing compound as a component imparting flame retardancy. As the phosphorus-containing compound, those which are reactive or may be added. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixyl phosphate, cresyl diphenyl phosphate, and cresyl-2,6-di phosphate. Xylylene ester, 1,3-phenylene bis(dixyl phosphate), 1,4-phenylene bis(dimethoate), 4,4'-biphenyl (dylenecyl phosphate) Phosphate-based compound; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide), phosphine such as 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide a phosphorus-containing epoxy compound, red phosphorus or the like obtained by reacting an epoxy resin with active hydrogen of the above phosphine, preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably 1,3- Phenyl bis(dixyl phosphate), 1,4-phenylene bis(xylylene phosphate), 4,4'-biphenyl (dicylene phosphate) or phosphorus-containing epoxy compound.

However, the amount of the phosphate ester compound to be used as described above is preferably a phosphate ester compound/epoxy resin ≦ 0.1 (weight ratio) for fear of environmental problems and electrical characteristics. Further, it is preferably 0.05 or less. It is particularly preferable to add a phosphorus-based compound in addition to being added as a curing accelerator.

The epoxy resin composition of the present invention may also contain an inorganic filler. Examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, calcium carbonate, calcium citrate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, cerium oxide, cerium oxide, and titanium oxide. , aluminum nitride, tantalum nitride, boron nitride, mica, glass, quartz, mica, and the like. Further, in order to impart a flame retarding effect, it is also preferred to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide. However, it is not limited to these. Further, two or more kinds may be used in combination. Among these inorganic fillers, cerium oxide such as molten cerium oxide or crystalline cerium oxide is preferable because it is inexpensive and has good electrical reliability. In the epoxy resin composition of the present invention, the inorganic filler is used in an amount of usually 60% by weight to 95% by weight, preferably 70% by weight to 95% by weight, more preferably 75% by weight to 90% by weight. The range of %. If it is 60% by weight or more, the effect of flame retardancy is surely obtained, and if it is 95% by weight or less, the half of the seal will be obtained. When the conductor element is mounted on the copper lead frame, the linear expansion ratio of the sealing resin and the frame is surely matched, and it is difficult to cause an abnormality due to thermal stress such as thermal shock.

The epoxy resin composition of the present invention can be formulated with a release agent for good mold release from the mold during molding. As the release agent, any of the conventionally known ones may be used, and examples thereof include ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, oxidized polyethylene, and non-oxidation. A polyolefin wax such as polyethylene. These may be used alone or in combination of two or more. The amount of the release agent to be added is preferably from 0.5 to 3% by weight based on the total of the organic components. When it is 0.5% by weight or more, the release from the mold does not deteriorate, and if it is 3% by weight or less, it does not deteriorate with the lead frame or the like.

In the epoxy resin composition of the present invention, a coupling agent can be blended in order to improve the adhesion between the inorganic filler and the resin component. As the coupling agent, any of the conventionally known ones can be used, and examples thereof include a vinyl alkoxy decane, an epoxy alkoxy decane, a styryl alkoxy decane, and a methacryloxy alkoxy decane. Various alkoxydecane compounds such as propylene methoxy alkoxy decane, amino alkoxy decane, mercapto alkoxy decane, and isocyanato alkoxy decane, alkoxide titanium compounds, aluminum chelate compounds, and the like. These may be used alone or in combination of two or more. In the method of adding the coupling agent, the surface of the inorganic filler may be treated with a coupling agent in advance, and then kneaded with the resin, or the coupling agent may be mixed in the resin, and then the inorganic filler may be kneaded.

Further, in the epoxy resin composition of the present invention, a known additive can be formulated as needed. Specific examples of the additives that can be used include: Polybutadiene and its modified substance, modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimine, fluororesin, maleimide compound, cyanate ester A compound, a polyoxymethylene gel, a polyoxygenated oil, and a coloring agent such as carbon black, phthalocyanine blue, or phthalocyanine green.

The epoxy resin composition of the present invention can be produced by any of the previously known methods which can uniformly disperse and mix the components. For example, all the components are pulverized and pulverized, and mixed by a Henkel mixer or the like, and then melt-kneaded by a heating roll, melt-kneaded by a kneader, mixed by a special mixer, or an appropriate combination of the respective methods. Thereby, preparation is carried out. Moreover, the semiconductor device mounted on the lead frame or the like is resin-sealed by transfer molding or the like using the epoxy resin composition of the present invention, whereby a semiconductor device can be manufactured.

The semiconductor device has a cured product of the epoxy resin composition of the present invention such as the epoxy resin composition sealed by the above-described present invention. Examples of the semiconductor device include DIP (Dual inline package), QFP (Quad Flat Package), BGA (Ball Grid Array), and CSP (Chip Scale Package). , wafer size package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package, thin quad flat package).

Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

Here, the measurement conditions of each physical property value are as follows.

. ¹³ C-NMR

Measuring device: VARian NMR system 400 MHz

Solvent: chloroform

. Epoxy equivalent

The measurement was carried out in the manner described in JIS K-7236, and the unit was g/eq.

. Softening Point

The measurement was carried out in accordance with the method of JIS K-7234, and the unit was °C.

. Elastic modulus (DMA)

Dynamic viscoelasticity tester: TA-instruments, DMA-2980

Measuring temperature range: -30~280°C

Heating rate: 2 ° C / min

Test piece size: use a cut of 5mm × 50mm (thickness of about 800μm)

Tg: The peak point of Tan-δ in the DMA measurement was taken as Tg.

. Water absorption rate

Weight increase rate (%) of a disc-shaped test piece having a diameter of 5 cm × a thickness of 4 mm after boiling in water at 100 ° C for 72 hours

Example 1

Adding a naphthol-cresol novolak resin to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while adding a naphthol-cresol novolak resin (a naphthol and a cresol in the reaction of naphthol and cresol) 70 parts by weight, a resin obtained by reacting α-naphthol in 5% by weight of all naphthol, a softening point of 110 ° C), 160 parts, and 370 parts of epichlorohydrin (4 molar equivalent to phenol resin) 37 parts of dimethyl hydrazine were dissolved under stirring and heated to 40 to 45 °C. Then, it takes 90 minutes to add flaky hydrogen in batches. After 41 parts of sodium oxide, the reaction was further carried out at 40 ° C for 2 hours, and further at 70 ° C for 1 hour. After completion of the reaction, water was washed with 500 parts of water, and excess solvent such as epichlorohydrin was removed from the oil layer by distillation using a rotary evaporator under reduced pressure. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 °C. 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the methyl isobutylate was distilled off from the obtained solution under reduced pressure using a rotary evaporator. Thus, 196 parts of the epoxy resin (EP1) of the present invention was obtained.

The epoxy equivalent of the obtained epoxy resin was 233 g/eq., the softening point was 93 ° C, and the melt viscosity at 150 ° C (IC1 melt viscosity cone #1) was 1.3 Pa. s. Further, in the ¹³ C-NMR, the ratio of the total area of the peaks of 74 to 76 ppm to the total area of the peaks of 68 to 71 ppm was 64:36.

Synthesis Example 1

282 parts of β-naphthol was dissolved in 600 parts of methyl isobutyl ketone, and 53 parts of 30% by weight of sodium hydroxide was added. 67 parts of p-formaldehyde was added to the solution, and the mixture was reacted at 20 ° C for 3 hours. After completion of the reaction, 35% hydrochloric acid was added to make it neutral (pH 6 to 7), whereby a solution containing β-naphthol 1-hydroxymethyl group was obtained.

After 108 parts of o-cresol was added to the obtained solution, 2 parts of 35% hydrochloric acid was added, and the mixture was reacted at 30 ° C for 1 hour, and further at 70 ° C for 6 hours. Thereafter, the mixture was washed with water until the reaction liquid became neutral, and a solvent or the like was distilled off from the organic layer to obtain 420 parts of a comparative NCN resin. The obtained resin had a softening point of 90 ° C and a hydroxyl equivalent of 140 g / eq.

Synthesis Example 2

In Example 1, 140 parts of the NCN resin obtained in Synthesis Example 1 was used instead of the naphthol-cresol novolak resin, and an epoxy resin was synthesized in the same manner.

The obtained epoxy resin has an epoxy equivalent of 210 g/eq., a softening point of 68 ° C, and a melt viscosity of 0.12 Pa at 150 ° C. s (EP2). Further, in the ¹³ C-NMR, the ratio of the total area of the peaks of 74 to 76 ppm to the total area of the peaks of 68 to 71 ppm was 81:19.

Test example 1~10

For the epoxy resin obtained above and various epoxy resins shown in Table 1 below, the same equivalent amount of phenol novolac was formulated with respect to the epoxy equivalent of 1 molar equivalent (softening point 83 ° C, hydroxyl equivalent 106 g /eq) As a curing agent, 1 part by weight of triphenylphosphine as a catalyst is blended with respect to 100 parts by weight of the epoxy resin, and uniformly mixed/kneaded using a mixing roll to obtain a sealing epoxy Resin composition. The epoxy resin composition was pulverized by a stirrer and further flaky by a tableting machine. The sheet-form epoxy resin composition was subjected to transfer molding (175 ° C × 60 seconds), and after demolding, it was hardened under conditions of 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet.

Further, the details of the epoxy resin used in the evaluation are shown in Table 2 below.

As is apparent from Fig. 1, the use of a cured epoxy resin (Test Examples 2 to 9) basically has a relationship in which the water absorption rate increases as the Tg rises. On the other hand, it was confirmed that the cured product using the epoxy resin of the present invention has high heat resistance, but the water absorption rate is low, and the correlation is largely deviated.

The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on Sep. 8, 2011 (Japanese Patent Application No. 2011-195585). Moreover, all of the reference frames cited herein are incorporated as a whole.

[Industrial availability]

The epoxy resin of the present invention can be used for an epoxy resin composition which can simultaneously obtain a heat-resistant and water-resistant cured material for an insulating material for electrical and electronic parts and a laminate (printed circuit board, build-up substrate) Etc.) or various composite materials, adhesives, coatings, etc., including CFRP. In particular, it is extremely useful for protecting a semiconductor sealing material or a laminate material for a semiconductor element.

Figure 1 is a graph showing the results of the examples.

Claims (5)

An epoxy resin obtained by glycidylating a naphthol-cresol novolac type phenol resin, wherein the naphthol-cresol novolak type phenol resin is reacted with naphthol and cresol with an aldehyde. When the naphthol is reacted with cresol and aldehyde, the ratio of α-naphthol in the naphthol is 1 to 10% by weight, and the number average molecular weight Mn of the epoxy resin is 500 to 1000 (weight average molecular weight Mw)/ (Quantum average molecular weight Mn) is from 1.4 to 2.5. For example, in the epoxy resin of the first aspect of the patent application, wherein the above naphthol-cresol novolac type phenolic resin, the weight ratio of naphthol to cresol when reacting naphthol with cresol and aldehyde is 65:35-85: 15. The softening point of the naphthol-cresol novolac type phenol-based resin obtained is from 100 ° C to 150 ° C. For example, in the epoxy resin of claim 1 or 2, in ¹³ C-NMR, the total area of the peaks of 74 to 76 ppm and the total of the peaks of 68 to 71 ppm are 60:40 to 80: 20, and the softening point is 85 ° C ~ 100 ° C. An epoxy resin composition comprising the epoxy resin and a hardening accelerator according to any one of claims 1 to 3. A hardened material obtained by hardening an epoxy resin composition of claim 4 of the patent application.