KR101882720B1 - Epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Abstract

An epoxy resin and an epoxy resin composition which give a cured product having high heat resistance and excellent water absorption and electrical characteristics. The epoxy resin is obtained by reacting naphthol and cresol with aldehyde, and the ratio of? -Naphthol in the naphthol when the naphthol and cresol are reacted with aldehyde is 1 to 10% by weight. The naphthol-cresol novolak phenol resin By glycidylation. The naphthol-cresol novolak type phenolic resin has a weight ratio of naphthol to cresol of 65:35 to 85:15 when naphthol and cresol are reacted with aldehyde, and the obtained naphthol-cresol novolak type phenol resin has a softening point of 100 Deg.] C to 150 [deg.] C.

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 imparts a cured product excellent in heat resistance and water resistance.

BACKGROUND ART Epoxy resin compositions are widely used in the fields of electric and electronic parts, structural materials, adhesives, and paints due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance)

In recent years, however, in the field of electric and electronic fields, in accordance with the development of the resin composition, the viscosity of the resin composition has been increased, and the viscosity, adhesiveness, dielectric properties, low viscosity for high filling of the filler (inorganic or organic filler) The improvement of the characteristics of the semiconductor device is required to be further improved. In addition, as a structural material, a lightweight material having excellent mechanical properties is required for use in aerospace materials, leisure and sporting equipment, and the like. Particularly in the field of semiconductor encapsulation and the substrate (the substrate itself or the peripheral material thereof), the required characteristics thereof are becoming higher each year, and for example, a higher Tg of the peripheral material is required due to an increase in the driving temperature of the semiconductor have.

When the epoxy resin is generally made into high Tg, the water absorption rate increases (Non-Patent Document 1). This is an effect of improving the crosslink density. However, there has been an urgent need to develop a resin having the opposite characteristics, while demanding high Tg for a semiconductor peripheral material requiring low moisture absorption.

Also, similarly, when the high Tg is generally converted, the electrical reliability tends to decrease. That is, the dielectric constant and dielectric loss tangent deteriorate. It is necessary to lower the dielectric constant and dielectric tangent while maintaining a high Tg in the development of electric and electronic materials in view of improvement of electrical reliability.

 Ichiro Ogura, " Relationship between Chemical Structure and Properties of Epoxy Resin ", DIC Technical Review No. 7, Japan, 2001, page 7

The present invention has been made in order to solve such a problem, and it is intended to provide an epoxy resin whose cured product has high heat resistance, low water absorption and low dielectric constant.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have completed the present invention.

That is,

(1) a naphthol-cresol novolak type phenol resin obtained by reacting naphthol and cresol with an aldehyde, wherein the ratio of? -Naphthol in the naphthol when the naphthol and cresol are reacted with aldehyde is 1 to 10% An epoxy resin obtained by glycidylating an epoxy resin,

(2) The naphthol-cresol novolak type phenolic resin according to (1), wherein the weight ratio of naphthol to cresol when reacting naphthol and cresol with aldehyde is 65:35 to 85:15, Wherein the novolac-type phenol resin has a softening point of 100 占 폚 to 150 占 폚,

(3) The magnetic recording medium according to item (1) or (2), wherein the total amount of the peak area of 74 to 76 ppm and the peak area of 68 to 71 ppm in the ¹³ C-NMR is 60:40 to 80:20, Is 85 DEG C to 100 DEG C,

(4) The epoxy resin composition according to any one of (1) to (3), wherein the epoxy 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 an epoxy resin according to any one of (1) to (4) and a curing accelerator,

(6) A cured product obtained by curing the epoxy resin composition according to (5).

(Effects of the Invention)

The epoxy resin composition using the epoxy resin of the present invention is a cured product which can simultaneously achieve a heat resistance and a water resistance, and can be used as an insulating material for electrical and electronic parts, a laminated board (printed wiring board, build- Materials, adhesives, paints and the like. And is particularly useful for a semiconductor sealing material or a laminate material for protecting semiconductor devices.

1 is a graph showing the results of the embodiment.

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

The naphthol-cresol novolak type phenolic resin (NCN) obtained by reacting naphthol and cresol with aldehyde and having a ratio of? -Naphthol in the naphthol when the naphthol and cresol are reacted with aldehyde is not particularly limited However, for example, the following formula (1)

R represents a methyl group or a hydrogen atom, and Ar represents 1-naphthol, 2-naphthol, 2-naphthol, Cresol).

NCN is usually obtained by reacting naphthol, cresol and formaldehyde (or equivalents thereof) under acidic or basic conditions.

Concretely, it can be obtained by adding naphthol, cresol and formaldehyde (or an equivalent thereof) and a catalyst simultaneously or sequentially, and carrying out the reaction usually at 0 to 150 캜, preferably 10 to 130 캜. Here, by performing the reaction at a low temperature, it is also possible to preferentially proceed the reaction with naphthol.

At this time, if it is 0 DEG C or higher, the progress of the reaction does not become slow, it does not take much time, and the productivity is excellent, which is preferable. When the temperature is 150 ° C or lower, the reaction does not progress at once, and naphthol not involved in the reaction does not increase. The reaction is carried out within the above-mentioned range, whereby naphthol is relatively preferentially used, whereby a compound having a small residual naphthol content can be obtained.

The reaction time is usually 5 to 150 hours.

The NCN thus obtained may be used without purification depending on the application. Usually, the reaction mixture is neutralized after completion of the reaction and then purified by removing unreacted raw materials and solvents under heating and decompression. The neutralization step may be carried out by adding various bases, salts such as phosphates, buffers or the like, or by washing with water or the like. When the naphthol is not sufficiently consumed by the reaction, it is preferable that the residual naphthol content is made 1% or less by thin film distillation, bubbling of an inert gas such as nitrogen or the like.

Examples of the solvent that can be used in the synthesis of NCN include methanol, ethanol, propanol, isopropanol, toluene, xylene, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like, More than one species may be used. When a solvent is used, its amount is usually in the range of 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total amount of naphthol and cresol.

As the catalyst, either acidic or basic catalysts can be used.

Specific examples of the acidic catalyst that can be used include minerals such as hydrochloric acid, sulfuric acid, and phosphoric acid; Organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; Acidic catalysts commonly used for the production of novolak resins such as organic and inorganic acid salts exhibiting other acidity, such as heteropolyacid such as tungstic acid, activated clay, inorganic acid, stannic chloride, zinc chloride, ferric chloride and the like .

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, sodium methoxide, sodium ethoxide, potassium methoxide, Sodium and potassium-tert-butoxide; alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide; and the like.

An amine-based catalyst may also 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 to be used is generally in the range of 0.005 to 2.0 moles, preferably 0.01 to 1.1 moles per mole of the total amount of naphthol and cresol. When the catalyst is used as a solvent, it is preferable to add about 30 to 200% by weight based on the total amount of naphthol and cresol.

Thus, the naphthol-cresol novolak type phenol resin obtained by reacting naphthol with cresol and formaldehyde is obtained by random polymerization, so that the naphthalene skeleton and the phenol skeleton are randomly arranged.

In the present invention, naphthol may be used in combination with? -Naphthol and? -Naphthol, and cresol may be used in the form of orthocresol, metacresol, paracresol, or any combination of two or more thereof.

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

The weight ratio of naphthol to cresol used in the reaction is preferably 65:35 to 85:15, more preferably 62:38 to 80:20, and particularly preferably 62:38 to 76:24. On the other hand, a preferable ratio for exhibiting the characteristics of high heat resistance and low absorption is 71:29 to 85:15. When the amount of naphthol is 62% by weight or more, it is preferable to exhibit desired high heat resistance and low moisture absorption characteristics. When the amount of naphthol is 85% by weight or less, control of the reaction is facilitated and residual naphthol is reduced. Residues of naphthol are not desirable due to the odor, toxicity and heat resistance of the cured product.

In the present invention, the ratio of? -Naphthol to? -Naphthol in naphthol when naphthol and cresol are reacted with aldehyde is 1 to 10% by weight based on the total amount of naphthol. When α-naphthol is less than 1% by weight, the heat resistance does not rise, and when α-naphthol exceeds 10% by weight, it is difficult to control the reaction and the amount of naphthol remaining is increased. There is also a method of controlling the molecular weight and reducing residual naphthol by condensation after naphthol or cresol methylolization followed by condensation. However, this method is troublesome in production and poor in productivity, and is not preferable.

It is preferable that the NCN at this time has a softening point of 100 to 150 캜. This skeleton is characterized by its molecular weight, and it is easy to exhibit the intended heat resistance if there is a linkage of molecules having a softening point of 100 ° C or higher. When the softening point is 150 캜 or lower, it is easy to handle, and it is easy to reduce the residual naphthol. Further, the residue of naphthol is not desirable for the safety of the user. In the present invention, at least 1% is important.

The NCN is glycidylated to obtain the epoxy resin of the present invention.

In order to glycidylate the NCN, it is preferable to react the NCN with epihalohydrin.

Examples of the epihalohydrin used in the reaction of NCN and epihalohydrin include epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, epibromohydrin and the like, In the present invention, epichlorohydrin which is industrially available is preferable. The amount of epihalohydrin to be used is usually 3.0 to 10 mol, preferably 3.5 to 8 mol, per 1 mol of the hydroxyl group of NCN.

In the epoxidation reaction, it is preferable to use an alkali metal hydroxide. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Further, the alkali metal hydroxide may be used as a solid matter or an aqueous solution thereof. For example, in the case of using an alkali metal hydroxide as an aqueous solution, an aqueous solution of an alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or atmospheric pressure, The epoxidation reaction can be carried out by removing water and continuously returning the epihalohydrin into the reaction system. When a solid is used, it is preferable to use a flake form in view of handling easiness and solubility. The amount of the alkali metal hydroxide to be used is generally 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, and more preferably 0.99 to 1.15 moles, per 1 mole of the hydroxyl group of NCN.

In the epoxidation reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is preferably added as a catalyst in order to accelerate the reaction. The amount of the quaternary ammonium salt to be used is 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, alcohols such as methanol, ethanol and isopropyl alcohol, and aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane are preferably added to proceed the reaction.

When the alcohols are used, the amount of the alcohols to be used is usually from 2 to 50 mass%, preferably from 4 to 20 mass%, based on the amount of epihalohydrin used. On the other hand, when the aprotic polar solvent is used, its amount to be used is usually 5 to 100 mass%, preferably 10 to 80 mass%, based on the amount of epihalohydrin used.

The reaction temperature in the epoxidation reaction is usually from 30 to 90 캜, preferably from 35 to 80 캜. On the other hand, the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. The reactants of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, etc., after water washing or without heating under reduced pressure. In order to obtain an epoxy resin having little hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, And the ring-opening of the halohydrin as a by-product can be made definite.

In this case, the amount of the alkali metal hydroxide to be 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 for epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

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

The epoxy resin thus obtained preferably satisfies the following conditions. The softening point is preferably 80 to 100 占 폚, more preferably 85 to 100 占 폚, particularly preferably 85 to 97 占 폚. In order to obtain a preferable softening point, it can be adjusted according to the weight ratio of naphthol, cresol, and formalin (or a synthetic equivalent thereof) used in the reaction. The naphthol and cresol can be realized by applying the above- Preferably 0.5 to 1.1 moles, more preferably 0.60 to 1.1 moles, based on the equivalent weight. The formalin may be added in a batch or in a divided manner.

The epoxy equivalent is preferably 200 to 300 g / eq., More preferably 210 g / eq. To 260 g / eq. The epoxy equivalent is controlled by the amount of epihalohydrin used in the reaction, the amount of naphthol, the amount of cresol, and the molecular weight of the starting material, and the epoxy resin of the present invention having a preferred epoxy equivalent weight has a molecular weight determined by the method described in the above- The same method is employed, and the amount of epihalohydrin can be obtained by applying the above-described preferable amount.

The total amount of the peak area of 74-76 ppm and the peak area of 68-71 ppm in ¹³ C-NMR is preferably 60:40 to 80:20. 74 to 76 ppm and 68 to 71 ppm corresponds to the peak of the methylene moiety bonded to the oxirane structure of the glycidyl group bonded to the naphthol or cresol structure, respectively.

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

The number average molecular weight is preferably 500 to 1000, more preferably 500 to 800. The weight average molecular weight is preferably 600 to 2,000, more preferably 600 to 1,700. In order to obtain the epoxy resin of the present invention having a preferable average molecular weight, it can be adjusted by the weight ratio of naphthol, cresol and formalin (or a synthetic equivalent thereof) used in the reaction. When the amount of formalin to naphthol and cresol is small, And the smaller the epihalohydrin, the larger the molecular weight can be.

If the molecular weight is too small, heat resistance is not obtained. If the molecular weight is too large, the viscosity becomes too high, which makes handling difficult and also insufficient in solvent.

In the present invention, the molecular weight distribution becomes important. When the molecular weight distribution is too narrow, improvement in heat resistance and decrease in water absorption can not be expected. This is because the improvement of the heat resistance due to the crosslinking density at the time of crosslinking at the thermosetting step affects the increase of the absorptivity in terms of giving hydroxyl groups at the time of crosslinking. In the present invention, not only the heat resistance but also the water absorption can be lowered by increasing the number of bonds in the methylene chain in the parent skeleton.

The specific molecular weight distribution (weight average molecular weight (Mw)) / (number average molecular weight (Mn)) is preferably 1.4 or more. When the molecular weight distribution is too large, problems such as an excessively high viscosity occur. 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 addition of formalin can be made narrower by the addition of divided portions. By decreasing the amount of epihalohydrin, the molecular weight distribution can be widened. On the contrary, the molecular weight distribution can be narrowed. Further, in the production of NCN, it is also possible to broaden the molecular weight distribution by performing rearrangement reaction in which the methylene bond is once cleaved at 80 to 150 ° C and then bonded again. In the rearrangement, it is preferable to add 0.005 to 0.1 equivalent of formalin (or a synthetic equivalent thereof) to 1 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 the whole epoxy resin is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

Representative examples of the other epoxy resins include novolak type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins and the like.

Specific examples of other epoxy resins that can be used in combination 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, Dihydroxybenzene, dihydroxy naphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthalaldehyde, glue Aldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); The phenols and various diene compounds (dicyclopentadiene, terpene, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, Butadiene, isoprene, etc.); Polycondensates of the phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); Polycondensates of the phenols and aromatic dimethanol (benzene dimethanol, biphenyl dimethanol, etc.); Polycondensates of the phenols with aromatic dichloromethyls (a, a'-dichloro xylene, bischloromethylbiphenyl, etc.); Polycondensates of the phenols with aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylation of bisphenols and various aldehydes or alcohols, etc. , And epoxy resin which is usually used. These may be used alone, or two or more of them may be used.

Examples of the curing agent contained in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, an amide compound, a phenol compound, and a carboxylic acid compound. Specific examples of the curing agent that can be used include amine-based compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; Amide compounds such as dicyandiamide, a polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; Acid anhydride-based compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 (4-hydroxyphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p- hydroxybenzaldehyde, o-hydroxybenzaldehyde, p A reaction product of phenol or cresol with a phenylene dimethylol derivative, dimethoxymethyl derivative or methyl halide, or a reaction product of phenol, cresol and bis Chloromethylbiphenyl, bismethoxymethylbiphenyl or bishydroxymethylbiphenyl, or a reaction product of phenol A phenol aralkyl resin which is a reaction product of benzene diisopropanol, benzene diisopropanol dimethyl ether or benzene bis (chloroisopropane), modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols Phenol compounds, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, and the like, but are not limited thereto. These may be used alone, or two or more of them may be used.

In the present invention, from the viewpoint of heat resistance, chemical resistance and electrical reliability, it is preferable to use a phenol compound as a curing agent. Particularly, from the flame retardancy, novolak resins, in particular phenol novolac resins or cresol novolac resins, . In the present invention, it is preferable to use a curing agent having a softening point of 50 to 100 캜. When the softening point is low, the flowability and flame retardancy tend to be improved, but it is preferable to use one having a high softening point in order to improve the heat resistance.

The amount of the curing agent to be used in the epoxy resin composition of the present invention is preferably 0.8 to 1.1 equivalents based on 1 equivalent of the epoxy group of the epoxy resin. 0.8 equivalents or more, or 1.1 equivalents or less, based on one equivalent of the epoxy group, are all preferable because the curing is complete and good curing properties are obtained. In the present invention, preferred combinations of the epoxy resin and the curing agent are an epoxy resin having a softening point of 45 to 70 캜 (more preferably 50 to 65 캜) and a curing agent having a softening point of 50 to 100 캜 (preferably 55 to 85 캜). It is a resin composition having properties that are balanced in terms of fluidity, flame retardancy, and heat resistance.

The epoxy resin composition of the present invention may contain a curing accelerator. Specific examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as diazabicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing 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.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be of the reaction type or of the addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylallylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicyclylenyl phosphate, Dicyclylenylenylphosphate), 1,4-phenylenebis (dicyclylenylenylphosphate), and 4,4'-biphenyl (dicyclylenylenylphosphate); Oxides such as 9,10-dihydro-9-oxa-10-phosphoperanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphoperanthrene- ; Containing epoxy compound obtained by reacting an epoxy resin with active hydrogens of the phosphates, and red phosphorus. Of these, phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis Silylenyl phosphate), 1,4-phenylenebis (dicyclylenylenylphosphate), 4,4'-biphenyl (dicyclylenylphosphate) or phosphorus-containing epoxy compounds are particularly preferable.

However, from the viewpoint of environmental problems and electric characteristics, the amount of the phosphoric acid ester compound used is preferably phosphoric acid ester compound / epoxy resin =? 0.1 (weight ratio). More preferably 0.05 or less. Particularly preferably, a phosphorus compound is not added, except that it is added as a curing accelerator.

The epoxy resin composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, boron nitride, Glass, quartz, mica, and the like. It is also preferable to use metal hydroxides such as magnesium hydroxide and aluminum hydroxide for imparting a flame retarding effect. However, the present invention is not limited thereto. Two or more kinds may be mixed and used. Among these inorganic fillers, fuels such as fused silica and crystalline silica are preferable because they are inexpensive and have good electrical reliability. The amount of the inorganic filler to be used in the epoxy resin composition of the present invention is usually from 60% by weight to 95% by weight, preferably from 70% by weight to 95% by weight, and more preferably from 75% by weight to 90% by weight. When the amount of the sealing resin is less than 95% by weight, the linear expansion coefficient of the sealing resin and the frame can be reliably matched when the sealing semiconductor element is mounted on the copper-based lead frame, A problem due to stress is unlikely to occur.

In the epoxy resin composition of the present invention, a release agent may be blended in order to improve releasing from the mold during molding. As the release agent, any of conventionally known agents can 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, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene And the like. These may be used singly or in combination of two or more. The blending amount of these releasing agents is preferably 0.5 to 3% by weight based on the total organic components. If it is 0.5% by weight or more, the release from the mold is not deteriorated. If it is 3% by weight or less, adhesion with the lead frame and the like is not deteriorated.

A coupling agent may be added to the epoxy resin composition of the present invention in order to improve the adhesion between the inorganic filler and the resin component. As the coupling agent, any conventionally known one can be used. Examples of the coupling agent include vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryloxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanate alkoxy Various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used singly or in combination of two or more. The coupling agent may be added by kneading with a resin after the surface of the inorganic filler is treated with a coupling agent in advance, or by kneading an inorganic filler after mixing the coupling agent with the resin.

In the epoxy resin composition of the present invention, known additives may be added if necessary. Specific examples of usable additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone Gel, silicone oil, and coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green.

The epoxy resin composition of the present invention can be produced by any conventionally known method capable of uniformly dispersing and mixing each component. For example, by pulverizing and pulverizing each component, mixing the mixture with a Henschel mixer or the like, melting and kneading with a heating roll, melt kneading with a kneader, mixing with a special mixer, or any combination of these methods . In addition, a semiconductor device can be manufactured by using the epoxy resin composition of the present invention and sealing a semiconductor element mounted on a lead frame or the like by resin molding or the like.

The semiconductor device has a cured product of the epoxy resin composition of the present invention such as one encapsulated with the epoxy resin composition of the present invention. Examples of the semiconductor device include a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), an SOP (small outline package) ), TQFP (Sync Word Flat Package), and the like.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.

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

¹³ C-NMR

Measuring apparatus: VARian NMR system 400 MHz

Solvent: Chloroform

· Epoxy equivalent

Measured by the method described in JIS K-7236, and the unit is g / eq.

· Softening point

Measured by the method according to JIS K-7234, and the unit is ° C.

· Modulus of elasticity (DMA)

Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980

Measuring temperature range: -30 ~ 280 ℃

On rate: 2 ℃ / min

Specimen size: 5 mm × 50 mm cut out (thickness about 800 μm)

Tg: The peak point of Tan-delta in the DMA measurement was defined as Tg.

· Absorption Rate

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

Example 1

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with naphthol-cresol novolak resin (naphthol-cresol novolak resin (when naphthol and cresol were reacted with aldehyde in a naphthol and cresol 70 wt% (4 molar equivalents to the phenol resin) and 37 parts of dimethyl sulfoxide were added, and the mixture was dissolved under stirring, and the temperature was raised to 40 to 45 DEG C did. Subsequently, 41 parts of sodium hydroxide on the flakes was dividedly added over 90 minutes, and then the reaction was further carried out at 40 DEG C for 2 hours and at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed with 500 parts of water, and excess epichlorohydrin and other solvents were distilled off from the oil layer using a rotary evaporator under reduced pressure. 500 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. 10 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring, and the mixture was reacted for 1 hour. Thereafter, washing was carried out until the washing water in the oil layer became neutral. From the resultant solution, methyl isobutyl ketone And the like were distilled off to obtain 196 parts of the epoxy resin (EP1) of the present invention.

The epoxy equivalent of the obtained epoxy resin was 233 g / eq. The melt viscosity (ICI melt viscosity cone # 1) at a softening point of 93 占 폚 and 150 占 폚 was 1.3 Pa · s. The ratio of the total amount of the area of the peak of 74 to 76 ppm and the total area of the area of the peak of 68 to 71 ppm in < ¹³ > C-NMR was 64:36.

Synthesis Example 1

282 parts of? naphthol were dissolved in 600 parts of methyl isobutyl ketone, and 53 parts of 30 wt% sodium hydroxide was added. 67 parts of paraformaldehyde was added to this solution, and the reaction was carried out at 20 占 폚 for 3 hours. After completion of the reaction, 35% hydrochloric acid was added to neutralize (pH 6-7) to obtain a 1-methylol-containing solution of? -Naphthol.

108 parts of orthocresol was added to the obtained solution, 2 parts of 35% hydrochloric acid was added, and the reaction was carried out at 30 DEG C for 1 hour and at 70 DEG C for 6 hours. Thereafter, the reaction solution was washed with water until it became neutral, and the solvent or the like was distilled off from the organic layer to obtain 420 parts of comparative NCN resin. The resin obtained had a softening point of 90 占 폚 and a hydroxyl group equivalent of 140 g / eq.

Synthesis Example 2

An epoxy resin was synthesized in the same manner as in Example 1 except that 140 parts of the NCN resin obtained in Synthesis Example 1 was used instead of naphthol-cresol novolac resin.

The obtained epoxy resin had an epoxy equivalent of 210 g / eq. The melt viscosity at 150 캜 and the softening point of 68 캜 was 0.12 Pa · s (EP2). The ratio of the total area of the peak of 74-76 ppm and the total area of the peak of 68-71 ppm in < ¹³ > C-NMR was 81:19.

Test Examples 1 to 10

The epoxy resin obtained above and the various epoxy resins shown in Table 1 were compounded in equivalent equivalent amounts of phenol novolac (softening point 83 ° C, hydroxyl group equivalent 106 g / eq) as a curing agent with respect to one mole equivalent of epoxy equivalent, (Parts by weight) of phosphine in an amount of 1 part by weight based on 100 parts by weight of epoxy resin, and mixing and kneading were uniformly carried out using a mixing roll to obtain a sealing epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted by a tablet machine. The tableted epoxy resin composition was transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.

Details of the epoxy resin used in the evaluation are shown in Table 2 below.

Although it is clear from Fig. 1, the cured products (Test Examples 2 to 9) using a common epoxy resin basically have a correlation that the absorption rate increases when Tg rises. On the other hand, it was confirmed that the cured product using the epoxy resin of the present invention had a high heat resistance, but the water absorption rate was low and deviated greatly from the above relationship.

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

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2011-195585) filed on September 8, 2011, the entirety of which is incorporated by reference. In addition, all references cited herein are incorporated by reference in their entirety.

(Industrial availability)

The epoxy resin of the present invention can be used in an epoxy resin composition which gives a cured product capable of simultaneously achieving heat resistance and water resistance. The composition can be used as an insulating material for electrical and electronic parts, a laminated board (printed wiring board, build- And various kinds of composite materials, adhesives, paints and the like. And is particularly useful for a semiconductor sealing material or a laminate material for protecting semiconductor devices.

Claims (6)

Cresol novolak type phenolic resin obtained by reacting naphthol and cresol with an aldehyde and having a proportion of? Naphthol in the naphthol of 1 to 10% by weight when the naphthol and cresol are reacted with aldehyde is glycidylated, As the resin,
(Weight average molecular weight (Mw)) / (number average molecular weight (Mn)) of 1.4 to 2.5. The method according to claim 1,
In the naphthol-cresol novolak type phenol resin, the weight ratio of naphthol to cresol when reacting naphthol and cresol with aldehyde is 65: 35 to 85: 15, and the softening point of the naphthol-cresol novolak type phenol resin Lt; RTI ID = 0.0 > 100 C < / RTI > 3. The method according to claim 1 or 2,
Wherein the total amount of the peak area of 74 to 76 ppm and the peak area of 68 to 71 ppm in < ¹³ > C-NMR is 60:40 to 80:20 and the softening point is 85 to 100 ° C. . An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing accelerator. A cured product obtained by curing the epoxy resin composition according to claim 4.
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