TWI478955B - Epoxy resin composition, manufacturing method for the same, and cured article thereof - Google Patents

Description

Epoxy resin composition, method for producing the epoxy resin composition, and cured product thereof

The present invention relates to an epoxy resin composition which has both low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid hardening, and flame retardancy, a method for producing the same, and a cured product thereof.

The epoxy resin composition is widely used in electrical/electronic parts, structural materials, adhesives, paints, and the like because of its excellent electrical properties, heat resistance, adhesion, and moisture resistance.

However, in recent years, in the field of electrical/electronic materials, along with its development, it has been thought that the low viscosity of a large amount of filler fillers is the first, and it is required to be flame retardant, heat resistance, moisture resistance, adhesion, dielectric properties, and the like. Various features are improved. Although there are many proposals for the epoxy resin composition for such requirements, it has not been said to be sufficient. In particular, in the electronic circuit board material, defects such as cracking during the mounting and welding treatment are severely caused by moisture absorption, and thus the demand for a low moisture absorbing material becomes strong. In order to reduce the moisture absorption rate, it is necessary to fill the filler in a large amount, and in order to perform such a large amount of filling, it is necessary to make the resin composition low in viscosity. On the other hand, a carbon fiber reinforced composite material in which a carbon fiber excellent in specific strength and specific modulus of elasticity is used in a reinforcing fiber and an epoxy resin composition having good wettability and adhesion to the carbon fiber is used in a base resin is used. In addition, a resin composition having heat resistance at a low viscosity is also required.

When used in a single-sided sealed package such as a BGA (Ball Grid Array), the epoxy resin composition has excellent performance in that package warpage is small. However, in recent semiconductor packages, such as BGA, it has become finer pitch or has become a whole batch of sealed type, so in addition to warpage, high fluidity and adhesion to the substrate surface are required. Good and so on. Moreover, as long as it has a low melt viscosity, fluidity or adhesion can be improved, and a filler can be blended in a large amount, so that it is also advantageous in terms of solder heat resistance and water resistance. That is, in order to satisfy the characteristics of these sealing materials, it is strongly desired to have low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid hardening, and low flame viscosity of flame retardancy. An epoxy resin composition appeared.

Further, in order to build up an interlayer insulating material of a substrate, an epoxy resin composition excellent in water resistance and excellent in adhesion at a high glass transition temperature is also desired, and in order to achieve the object, the original water resistance or storage stability is achieved. An excellent phenolic hardener is expected to have both low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid hardening, and flame retardancy.

An epoxy resin is often used for the resin material for electronic materials, and various phenol novolac condensates, amines, and acid anhydrides are used as the hardener of the epoxy resin. In particular, as a curing agent for an epoxy resin for semiconductor (IC) sealing, a phenolic phenol aldehyde condensate is mainly used in terms of heat resistance and reliability. In recent years, the IC has been accumulating, the package is small, the film is thinned, or the surface mounting method is gradually applied. The sealing material is required to further improve the thermal shock resistance and the solder heat resistance during surface mounting work. The main factors affecting the heat resistance of the solder are the hygroscopicity of the resin material for sealing. In other words, the moisture-absorbing sealing material generates internal pressure due to vaporization of moisture at a high temperature during surface mounting work, and internal peeling or package cracking causes deterioration of solder heat resistance. Therefore, epoxy resins are particularly required to have low hygroscopicity.

In the epoxy resin varnish for printing substrate insulation, in view of the handleability at the time of manufacture of the prepreg, the viscosity is preferably as low as possible, and the amount of the organic solvent used is preferably as small as possible. However, the viscosity of the epoxy resin solution used in the field so far has a problem that it cannot be reduced to a sufficient degree, or it is difficult to reduce the amount of use of the organic solvent.

On the other hand, as a method of lowering the hygroscopicity of the sealing material, there is a method of adding a filler such as non-hygroscopic ceria which is filled in the sealing resin material. At this time, when the viscosity of the resin material of the base material is high, the high filling property of the filler is impaired, so that the viscosity of the epoxy resin is desired to be low. Further, the sealing material is required to have heat resistance, high strength, toughness, flame retardancy, adhesion strength, and the like. In the conventional sealing resin material which is a phenol phenol aldehyde condensate which is used as a hardening agent for a sealing epoxy resin, it is not highly hygroscopic and can be sufficiently satisfied from other physical properties.

Therefore, in order to improve low hygroscopicity, heat resistance, adhesion, flame retardancy, etc., there are proposals for various reactants of a phenol novolac condensate and its epihalohydrin. For example, a phenol aldehyde condensate of an alkylphenol such as o-cresol or a phenol aldehyde condensate of a naphthol such as 1-naphthol is used (for example, refer to Patent Documents 1 to 3). Further, a phenolic compound of di(hydroxypropyl)biphenyl which is a condensing agent for phenol (see Patent Document 4) and a phenol novolac condensate using a mixture of bis(methoxymethyl)biphenyl are disclosed. Proposal (refer to Patent Document 5). In addition, an epoxy resin molding material for sealing electronic parts using formaldehyde is disclosed (see Patent Document 6).

However, materials which further improve the hygroscopicity, heat resistance, adhesion characteristics, flame retardancy, rapid hardening, preservation stability, and the like are still desired.

[Previous Technical Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 59-230017

Patent Document 2: Japanese Laid-Open Patent Publication No. 05-078437

Patent Document 3: Japanese Patent Publication No. 05-086156

Patent Document 4: Japanese Laid-Open Patent Publication No. 05-117350

Patent Document 5: Japanese Laid-Open Patent Publication No. 08-143648

Patent Document 6: JP-A-63-022824

The object of the present invention is to provide low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid hardening, and flame retardancy, especially for electrical and electronic industries, sealing of electronic parts, An epoxy resin composition for a laminate material, a method for producing the epoxy resin composition, and a cured resin obtained from the epoxy resin composition.

In order to utilize the low hygroscopicity, high adhesion, and heat resistance of the above aralkyl type phenol resin, the present inventors have obtained an epoxy resin composition having a low melt viscosity, and have found through concentrating on the molecule. The present invention has both an alkylene-type polymer unit and a phenolic phenolic polymer unit, and the polymerization degree ratio of the two is in a specific range, thereby obtaining low melt viscosity and rapid hardening and low hygroscopicity, high adhesion, and heat resistance. The phenolic phenolic resin composition was excellent, and it was found that the same excellent epoxy resin composition can be obtained by the reaction of the obtained resin composition with an epihalohydrin, and the present invention has been completed.

In other words, the present invention is an epoxy resin composition containing a component represented by the following formula (1), and the content ratio of the compound represented by the following formula (3-1) and formula (3-2) is 50% or less.

General formula (1): (wherein R represents a group of the following formula (2-1) and formula (2-2): a cross-linking group of at least one of biphenylylene and xylylene (also referred to herein as "benzoyl"), and R ¹ , R ² and R ³ may be used. The same or different, each being a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, and p, q, and r are each an integer of 0 to 2. Further, m and n are positive numbers, and G represents glycidyl group).

General formula (3-1) and general formula (3-2): (wherein G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group).

Further, the present invention is an epoxy resin composition as described above, wherein m/n is from 0.04 to 20, and the melt viscosity at 150 ° C is from 10 to 200 mPa·s.

Further, the present invention provides a method for producing an epoxy resin composition, which comprises the following formula (4):

(wherein R represents a group of the following formula (2-1) and formula (2-2):

The cross-linking group of at least one of a biphenyl group and a benzene dimethyl group, R ¹ , R ² and R ³ may be the same or different, and each is a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. Or aryl, p, q, r are each an integer from 0 to 2. Further, the phenol resin composition of the component represented by m and n is a positive number is reacted with an epihalohydrin in the presence of an alkali metal hydroxide.

Further, the present invention is an epoxy resin cured product obtained by hardening the above epoxy resin composition.

Further, the epoxy resin composition of the present invention is an epoxy resin composition obtained by reacting a phenol resin composition with an epihalohydrin, and the phenol resin composition is represented by a formula (6-1) to be described later. A biphenyl compound and/or a benzene dimethyl compound represented by the formula (6-2), a phenol compound, and formaldehyde are reacted.

The epoxy resin composition of the present invention has a composition selected from the group consisting of 4,4′-extended biphenyl, 2,4′-extended biphenyl, 2,2′-extended biphenyl, etc. a biphenyl group; an epoxy resin having a crosslinking group of at least one of benzene dimethyl groups such as 1,4-benzenedimethyl, 1,2-benzenedimethyl, and 1,3-benzenedimethyl, and a polymerized unit of an epoxy resin containing a methylene crosslinking group and having a polymerization degree ratio of a specific range, and thus is suitable for an epoxy resin composition having both low melt viscosity, high glass transition temperature, and low suction. A resin composition having wettability, high adhesion, heat resistance, flame retardancy, storage stability, and good handling properties.

The resin composition of the present invention can be adapted to the most novel semiconductor sealing materials such as BGA.

The epoxy resin composition of the present invention uses an epihalohydrin to have a total of n phenol resins containing R represented by the above formula (4) as a stretching phenyl crosslinking group and/or a benzene dimethyl crosslinking group. An epoxy resin composition containing a component of the above formula (1) obtained by glycidyl etherification of a copolymerized unit and a copolymerized phenol resin composition of a total of m phenol resin polymerized units containing a methylene crosslinking group Further, the polymerization degree ratio m/n of each of the polymerized units in the formula (1) is preferably from 0.04 to 20, preferably from 0.05 to 9, more preferably from 0.1 to 6, and the melt viscosity at 150 ° C is 5 It is preferably an epoxy resin composition of 10 to 200 mPa ‧ to 1000 mPa ‧ s. The m/n is from 0.04 to 20, and the melt viscosity at 150 ° C is preferably from 10 to 200 mPa ‧ s.

The preferred range is the average molecular weight of the epoxy resin composition (the degree of polymerization differs depending on the molar ratio of the phenol compound used and the total amount of the crosslinked body constituting R of the formula (4) and formaldehyde). different.

The phenol resin composition represented by the above formula (4) is described in detail in JP-A-2008-189708.

The phenolic resin composition of the phenol compound used and the crosslinked body of the formula (4) and the total amount of formaldehyde used in the molar ratio of less than 2.0 to 3.0 times moles of the phenol resin composition is glycidylated. The epoxy resin composition has a melt viscosity at 150 ° C of 100 to 200 mPa ‧ s, more preferably 100 to 150 mPa ‧ s.

When the molar ratio of the phenol compound to be used and the crosslinked body constituting the R of the formula (4) and formaldehyde is 3.0 or more and less than 10 times the molar amount (preferably 3.0 to 5 times the molar amount) The epoxy resin composition obtained by glycidyl etherification of the phenol resin composition has a melt viscosity at 150 ° C of 10 to 100 mPa ‧ s, more preferably 30 to 80 mPa ‧ s.

In the epoxy resin composition of the present invention, the value of m/n is not particularly limited. However, when the value of m/n is less than 0.04, the effect of lowering the melt viscosity may be insufficient, and the fluidity may be deteriorated. Therefore, the value of m/n is preferably 0.04 or more. More preferably it is between 0.1 and 6. A preferred range of the molar ratio (phenol/(m+n)) of the phenol compound to the total amount of the crosslinked body of the formula (4) and formaldehyde is from 2.0 to 5, plus m of the condition A preferred value for /n is from 0.1 to 6, more preferably from 0.3 to 3.

The phenol compound used in the present invention is a compound group composed of the following formula (4): having at least one hydroxyl group in the benzene ring, and R ¹ , R ² and R ³ are the same. Different from each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and p, q and r are each an integer of 0 to 2. Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group such as a methyl group, an ethyl group or a propyl group; and a branched alkyl group such as an isopropyl group or a tributyl group; For example, a phenyl group or the like can be mentioned.

These phenol compounds are used alone or in combination of two or more kinds.

Specific examples of the phenol compound include, for example, a monohydric phenol such as phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, nonylphenol, xylenol or butylmethylphenol. : 2 phenols such as catechol, resorcinol and hydroquinone, and phenol is particularly preferred.

The present invention is preferably a formaldehyde as a compound which forms a methylene crosslinking group. Further, as the form of formaldehyde, there is no particular limitation, and an aqueous formaldehyde solution can be used; and paraformaldehyde, three A polymer such as trioxane which decomposes into formaldehyde in the presence of an acid.

It is preferably an aqueous formaldehyde solution which is easy to handle, and a commercially available 42% aqueous formaldehyde solution can be used as it is.

The crosslinking group R used in the present invention may, for example, be a 4,4'-extended biphenyl group, a 2,4'-extended biphenyl group represented by the formula (2-1) or the formula (2-2) or 2,2'-Extended biphenyl; 1,4-benzyldimethyl, 1,2-benzenedimethyl or 1,3-benzyldimethyl and the like. These isomers may be used singly or in combination.

These cross-linking groups are derived from the compounds represented by the following formulae (6-1) and (6-2).

(In the formula, wherein Y represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms).

Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is preferred. The alkoxy group is not particularly limited, and preferably an aliphatic alkoxy group having 1 to 6 carbon atoms is preferred.

Specific examples of the compound represented by the formulae (6-1) and (6-2) include 4,4'-bis(halomethyl)biphenyl and 2,4'-di(halomethyl)biphenyl. 2,2'-bis(halomethyl)biphenyl, 4,4'-bis(alkoxymethyl)biphenyl, 2,4'-bis(alkoxymethyl)biphenyl, 2,2' - bis(alkoxymethyl)biphenyl, 1,4-bis(halomethyl)benzene, 1,4-bis(alkoxymethyl)benzene, 1,2-bis(halomethyl)benzene, 1,2-bis(alkoxymethyl)benzene, 1,3-bis(halomethyl)benzene, and 1,3-bis(alkoxymethyl)benzene; or 4,4'-di ( Hydroxymethyl)biphenyl, 2,4'-bis(hydroxymethyl)biphenyl, 2,2'-bis(hydroxymethyl)biphenyl, 1,4-bis(hydroxymethyl)benzene, 1,3 - bis(hydroxymethyl)benzene, and 1,2-bis(hydroxymethyl)benzene.

Preferred examples of the compounds of the formulae (6-1) and (6-2) include, for example, 4,4'-bis(chloromethyl)biphenyl and 4,4'-di(methoxy). Methyl)biphenyl, 4,4'-bis(ethoxymethyl)biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1 , 4-bis(ethoxymethyl)benzene.

As the cross-linking body of R in the formula (4), there is no problem in that the biphenyl group and/or the benzoic acid group can be used singly or in combination. However, when used after mixing, the mixing ratio is preferably from 20 to 50 mol% of benzoyl groups relative to the extended biphenyl group. R is a biphenyl crosslinking group, and particularly preferably a 4,4'-extended biphenyl crosslinking group.

The conditions for producing the phenol resin composition are described in detail in JP-A-2008-189708, and therefore, it is only necessary to carry out the conditions according to the conditions.

An example of a process for producing a phenol resin composition represented by the formula (4) is disclosed below.

The content ratio of the phenol resin composition to the compound represented by the following formula (5-1) and formula (5-2) (when these are collectively referred to as "dual cores") is 50% or less based on the phenol resin. In particular, 47% is preferred, 5 to 47% is preferred, and 10 to 40% is preferred. Meanwhile, the content ratio of the compound represented by the general formula (5-1) and the general formula (5-2) is determined by the area ratio of the graph measured by gel permeation chromatography as described later.

(wherein R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group).

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁴ and R ⁵ of the formula (5-1) and the formula (5-2) include a linear alkane such as a methyl group, an ethyl group or a propyl group. Examples of the branched alkyl group such as an isopropyl group and a tributyl group, and examples of the aryl group include a phenyl group and the like.

[Manufacture of phenol resin composition]

The method for producing a phenol resin composition represented by the formula (4) is a method in which, in the presence of an acid catalyst, N is added in an amount of n times mole relative to a certain amount of the phenol compound (that is, 4, 4'- is contained). Strending biphenyl, 2,4'-extended biphenyl or 2,2'-biphenyl; and / or 1,4-benzyl, 1,2-benzenedimethyl or 1,3- The crosslinked product of benzenedimethyl or the like is reacted with m mole of formaldehyde to carry out a condensation reaction in one stage.

In this case, it is preferred that the amount of the phenol used is not particularly limited, but is preferably from 1.3 to 10, relative to 1 part of the total of the crosslinked body constituting R in the general formula (4) and formaldehyde. More preferably, it is used in the range of 2.0 to 5 times Mo, and at the same time, the reaction temperature is low (for example, at about 100 ° C), the reaction of the phenol compound with formaldehyde is preferentially performed, and the main low molecular weight is made. The phenol resin composition of the methylene crosslinked body is formed, and then, after raising the temperature or increasing the amount of the catalyst, the phenol resin composition of the methylene crosslinking group and the crosslinked body constituting R in the formula (4) are formed. And phenol reaction.

The acid catalyst to be used is not particularly limited, and two or more kinds of known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid may be used alone or in combination with sulfuric acid, oxalic acid, or p-toluenesulfonic acid. good.

The temperature of the condensation reaction is preferably from 50 to 120 ° C as the low temperature condition, preferably from 80 to 110 ° C, and the reaction temperature at the temperature rise is from 130 to 230 ° C, preferably from 150 to 200 ° C.

The time of the condensation reaction varies depending on the reaction temperature or the type and amount of the catalyst to be used, but it is about 1 to 24 hours.

The reaction pressure is usually carried out under normal pressure, but it does not cause any problem under a slight pressure or under reduced pressure.

When the amount of the phenol used is less than 1.3 times the molar amount of the crosslinked body constituting R in the general formula (4) and formaldehyde, there is a tendency to obtain a phenol resin composition having a high molecular weight and a high melt viscosity. .

In addition, when the amount of the phenol is more than 10 times the molar amount, the low molecular weight component below the dinuclear body is increased, and the decrease in Tg, the decrease in mechanical strength, and the like tend to lower the physical properties, and the amount of phenol is increased to increase the cost. The environmental load has become a problem. The amount of phenol used is preferably from 1.5 to 10 moles.

Meanwhile, the phenol resin composition used in the present invention is a phenol compound, formaldehyde, 4,4'-extended biphenyl group, 2,4'-extended biphenyl group or 2 constituting R in the formula (4). 2'-Exbiphenyl; and/or the order of addition of crosslinked bodies such as 1,4-benzyldimethyl, 1,2-benzenedimethyl or 1,3-benzyldimethyl is not limited, and economical In terms of productivity, it should be added at the same time.

Other methods include, for example, the formaldehyde of the crosslinked body and the 4,4'-extended biphenyl group, 2,4'-extended biphenyl group or 2,2'- which constitute R in the formula (4). A method in which a biphenyl group; and/or a crosslinked body such as 1,4-benzenedimethyl, 1,2-benzenedimethyl or 1,3-benzenedimethyl is added in a staggered manner.

Specifically, the phenol compound may be previously condensed with formaldehyde in the presence of an acid catalyst, followed by the addition of 4,4′-extended biphenyl, 2,4′-extended biphenyl group constituting R in the formula (4) or 2,2'-Exbiphenyl; and/or 2 or more condensations of condensed bodies such as 1,4-benzyldimethyl, 1,2-benzenedimethyl or 1,3-benzyldimethyl The reaction is made. In such a two-stage condensation reaction, a new phenol compound can be added to the reaction of the second stage. However, at this time, as in the case of the first-stage reaction, it is preferred to use an excess of the phenol compound. The phenol resin further added in the reaction of the second stage is a total of 1 mole of the crosslinked body of R in the formula (4) and the total amount of the formaldehyde in the reaction of the first to second stages, in the range of 1 to 2 The total amount of phenol fed in the stage is preferably 1.3 times or more, preferably 2.3 to 5 times the range of moles. When the two-stage reaction is carried out, the polymerization degree (i.e., n and m) of each of the polymerized units of the alkylene-containing crosslinked phenol resin and the methylene-containing crosslinked phenol resin is narrowed. It is preferred for the purpose of the present invention to easily control the molecular weight and to easily obtain a polymer having a desired melt viscosity.

However, it is also possible to use a phenol compound, a 4,4'-extended biphenyl group, a 2,4'-extended biphenyl group or a 2,2'-extended biphenyl group constituting R in the formula (4); Adding formaldehyde after the reaction of a crosslinked body such as 1,4-benzenedimethyl, 1,2-benzenedimethyl or 1,3-benzenedimethyl, but in this case, the total amount of the phenol compound is relative to When the total amount of the crosslinked body of R and the total amount of formaldehyde in the formula (1) is 1 to about 1.3 times, the polymerization proceeds, and the low viscosity does not proceed, but is produced. Not a good situation.

The 2-stage condensation reaction can be carried out according to the condensation reaction conditions of the first stage.

The amount of the acid catalyst used in the first-stage condensation reaction and the two-stage condensation reaction varies depending on the type thereof, but the case of oxalic acid is preferably about 0.1 to 2.0% by weight, and the case of sulfuric acid is preferably about 0.05 to 0.5% by weight. In the case of p-toluenesulfonic acid, it is preferred to use about 0.02 to 0.1% by weight. In particular, in the case of a two-stage condensation reaction, when a biphenyl group or a benzene dimethyl crosslinker having a second stage is reacted with a phenol compound and a methylene crosslinking phenol resin, sulfuric acid or p-toluene is used. Acid is better. Further, the reaction temperature is not particularly limited, and is preferably in the range of from about 60 to 160 ° C, more preferably from 80 to 140 ° C.

After the condensation reaction in the presence of an acid catalyst, the phenol resin composition used in the present invention can be obtained by removing the unreacted phenol compound and the acid catalyst.

The method of removing the phenol compound is generally a method of distilling off the phenol compound to the outside of the system while heating under reduced pressure or by feeding an inert gas. The removal of the acid catalyst is exemplified by a method of washing by washing or the like.

The epoxy resin composition of the present invention is required to have a content ratio of a compound represented by the following formula (3-1) and formula (3-2) (in the case of the general term "dual core"). The epoxy resin is below 50%. It is preferably 47% or less, preferably 5 to 47%, and particularly preferably 10 to 40%. Meanwhile, the content ratio of the compound represented by the general formula (3-1) and the general formula (3-2) is determined by the area ratio of the graph measured by gel permeation chromatography as described later.

(wherein G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group).

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁴ and R ⁵ include a linear alkyl group such as a methyl group, an ethyl group or a propyl group; and a branched alkyl group such as an isopropyl group or a tributyl group; Examples of the aryl group include a phenyl group and the like.

In the epoxy resin composition of the present invention, when the content ratio of the compound represented by the formula (3-1) and the formula (3-2) exceeds 50%, the viscosity increases to 150 in which the epoxy resin composition cannot be measured. The degree of ICI viscosity at °C. Therefore, the handling property of the epoxy resin composition is deteriorated.

[Manufacture of epoxy resin composition]

The method for producing an epoxy resin composition represented by the formula (1) is that the phenol resin composition represented by the formula (4) can be used in an epihalohydrin, in an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. In the presence of the product, glycidyl etherification is carried out at 10 ° C to 120 ° C. The glycidyl etherification can be carried out by a known method without particular limitation.

As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, or the like can be used, and an industrially easy-to-obtain chlorine which is easily reactive with a hydroxyl group can be used. Alcohol is preferred.

The amount of the epihalohydrin to be used is not particularly limited, and may be appropriately selected depending on the molecular weight of the intended epoxy resin. Usually, the epihalohydrin is used in an excess amount with respect to the phenol resin. Since the epoxy resin composition of the present invention is expected to have a low melt viscosity, the amount of epihalohydrin used is 3.0 to 20 moles, and preferably 3.0 to 10 moles, relative to the hydroxyl group of the phenol resin composition.

As the alkali metal hydroxide to be used, a solid matter can be used, or an aqueous solution thereof can also be used. When an aqueous solution is used, an aqueous solution of an alkali metal hydroxide may be continuously added to the reaction system on one side, and water and epihalohydrin may be continuously discharged to the outside of the reaction system under reduced pressure or under normal pressure to remove moisture. A method in which epihalohydrin is continuously returned to the reaction system. The alkali metal hydroxide is used in an amount of from 0.8 to 2.0 mol, and preferably from 0.9 to 1.3 mol, based on the hydroxyl group of the phenol resin composition.

When glycidyl etherification is carried out, an alcohol such as methanol, ethanol or isopropanol is added to the reaction; dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, and the like are added. It is preferred to carry out the reaction after an aprotic polar solvent such as a dioxane.

At the same time, tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride may be added as a catalyst to the mixture of the phenol resin composition represented by the general formula (4) and the epihalohydrin. A method in which a 4-stage ammonium salt is added to an alkali metal hydroxide by a halogenated alcohol etherate obtained by such a reaction to form a ring closure.

The reaction temperature is not particularly limited and is usually from 30 to 90 ° C, preferably from 35 to 80 ° C.

Although the reaction time is also affected by the reaction temperature, it is usually from 0.5 to 10 hours, preferably from 1 to 8 hours.

After the reactants of the epoxidation reaction are washed with water or directly, the epihalohydrin or the solvent is removed under heating and reduced pressure without washing with water.

Further, in order to reduce the hydrolyzable chlorine, the recovered crude epoxy resin composition can be dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide is added to cause a reaction, and the ring closure is surely carried out.

After the completion of the reaction, the salt formed is removed by filtration, washing with water, etc., and the solvent is distilled off under reduced pressure under heating to obtain an epoxy resin composition of the formula (1) of the present invention.

A hardener and a hardening accelerator may be added to the epoxy resin composition of the present invention. The amount of the hardener added is preferably 5 to 40 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin. The amount of the hardening accelerator added is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

Hereinafter, a curing agent and a curing accelerator will be described.

[hardener]

Examples of the curing agent to be used include a phenol compound, an amine compound, an acid anhydride compound, and a guanamine compound.

Specific hardeners which can be used include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, polyalkylene glycol polyamine, diaminodiphenylphosphonium, isophor An amine-based curing agent such as ketone diamine; dicyandiamide; a guanamine-based hardener such as a polyamidene resin synthesized from a dilinoleic acid dimer and ethylenediamine; phthalic anhydride and benzene Tricarboxylic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, hexahydrobenzene An acid anhydride hardener such as methyl benzoate; phenol phenolic resin, cresol novolac resin, bisphenol A phenolic resin, bisphenol F phenolic resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene modified Phenolic resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, quaternary tetraphenoxy ethane resin, Naphthol phenolic resin, naphthol-phenol copolyphenolic resin, naphthol-cresol copolyphenol resin, biphenyl modification Resins, amine three A phenol resin-based curing agent represented by a modified phenol resin or the like; and such modified substances, imidazole, BF3-amine complex, and anthracene derivative, etc., but are not particularly limited thereto.

[hardening accelerator]

As the hardening accelerator, a conventional hardening accelerator for curing the epoxy resin composition with a phenol resin-based curing agent can be used. Examples of such a curing accelerator include an organic phosphine compound and a boron salt thereof, a tertiary amine, a 4- toluic ammonium salt, an imidazole, and a tetraphenylboron salt thereof, from the viewpoints of hardenability and moisture resistance. Preferably, triphenylphosphine and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU) are preferred. Further, in order to obtain higher fluidity, a curing accelerator which exhibits heat potential of activity by heating is more preferable, and a tetraphenylphosphonium derivative such as tetraphenylphosphonium tetraphenylborate is preferred.

[Other additives]

In the epoxy resin composition of the present invention, an inorganic filler, a release agent, a colorant, a flame retardant, a low stress agent, or the like may be added or pre-reacted as needed. Especially when used in semiconductor sealing, it is necessary to add an inorganic filler. Examples of such inorganic fillers include amorphous cerium oxide, crystalline cerium oxide, aluminum oxide, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, and magnesium oxide. And barium sulfate, etc., and amorphous cerium oxide, crystalline cerium oxide, etc. are preferred. These additives can be used in the same amount as in the conventional epoxy resin composition for semiconductor encapsulation.

[The cured product of epoxy resin composition]

The epoxy resin composition of the present invention can be used as a cured product. The cured product of the epoxy resin composition can be obtained by mixing the epoxy resin composition of the present invention, a phenol resin composition as a curing agent, and a hardening accelerator, and making the mixture at a temperature ranging from 100 to 250 ° C. Obtained by hardening.

Further, it is also possible to obtain a cured product by hardening the epoxy resin composition of the present invention in a temperature range of from 100 to 250 °C.

[Examples]

The invention will be specifically described below by way of examples. Further, the invention is not limited to the embodiments. Further, the evaluation method of the resin composition obtained by the present invention is shown below.

(1) Epoxy equivalent

Measured according to the method of JIS K-7236.

(2) 150 ° C melt viscosity: The melt viscosity of the epoxy resin composition at 150 ° C was measured using an ICI melt viscosity meter.

The method for measuring the viscosity of ICI is as follows.

ICI cone and plate viscometer Model CV-1S TOA Industrial Co., Ltd.

The plate temperature of the ICI viscometer was set at 150 ° C, and a predetermined amount of the sample was weighed. The weighed resin composition was placed on the plate portion, and pressed from the upper portion with a cone for 90 seconds. Rotate the cone and read this total value as the ICI viscosity.

(3) Gel Time test

The epoxy resin composition and the phenol resin composition were fed into the test tube in an equivalent amount of 1:1, and further, TPP was metered in an amount of 0.12 wt% with respect to the epoxy group, and fed into the test tube.

The test tube was placed in a gelation time timer (timer SF0-304M manufactured by Toshiba Co., Ltd.) in which the hot water temperature was set to 150 ° C and 175 ° C, and the mixture was rotated once in 1 second using a SUS stir bar.

Initially, the viscosity is low and it is liquid. After a certain period of time, the viscosity of the resin composition rapidly rises and becomes a gel. Let this time be the gel time. The faster this time, the better the indicator of hardenability.

(4) Water absorption rate

Each composition was injection molded at 150 ° C × 5 hours + 180 ° C × 3 hours, and was cured to have the following dimensions to prepare a sample.

Dimensions: ( Φ 50 ± 1) × (3 ± 0.2) (diameter × thickness; mm)

The surface of the above sample was wiped clean with a towel, and the weight of the sample was measured.

The above sample was placed in a 100 ml bottle, and 80 ml of pure water was added.

The bottle was placed in a hot air circulation drier at 95 ° C for 24 hours. The bottle was taken out from the hot air circulation drier and immersed in a low temperature constant temperature water bath to cool to 25 °C.

After cooling, the moisture adhering to the surface was wiped clean, and the weight was measured.

The water absorption rate was determined by the following formula.

Water absorption rate [%] = ((B-A) / A) × 100

A: weight before water absorption [g]

B: weight after water absorption [g]

(5) Tg (glass transition temperature)

Each of the compositions was injection-molded at 150 ° C for 5 hours + 180 ° C for 3 hours to be hardened, and the following dimensions were cut out to prepare a sample.

Dimensions: (50 ± 1) × (40 ± 1) × (100 ± 1) (longitudinal × horizontal × high; mm)

The sample was placed in a thermomechanical analyzer (TMA-60 (manufactured by Shimadzu)) and measured in an N ₂ atmosphere.

The measurement was carried out by raising the temperature to 350 ° C at a temperature increase rate of 5 ° C /min, and the temperature at the inflection point was determined and used as a glass transition temperature (Tg).

(6) Strength

It was measured according to the method of JIS K-7171.

(7) Spiral flow test

Using a low-pressure transfer molding machine, the EMC composition was injected in a spiral flow measurement die according to EMMI-1-66 at a die temperature of 175 ° C, an injection pressure of 6.8 MPa, and a dwell time of 120 seconds, and the flow length was measured. .

(8) Flame retardant (UL-94)

Measured according to the method of UL-94.

The detailed synthesis examples are listed below.

[Synthesis of phenol resin composition] Synthesis Example 1

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 564 g (6.00 mol) and 4,4'-bis(methoxymethyl)biphenyl were fed (hereinafter referred to as 4.4'- BMMB) 202.60 g (0.84 mol), 420.0% aqueous solution of Formalin 40.0 g (0.56 mol), 0.28 g of a 50% aqueous sulfuric acid solution, and reacted at 100 ° C for 3 hours.

Thereafter, the reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 330 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 39 mPa‧s, and the OH equivalent by the acetonitrile method was 166 g/eq.

Synthesis Example 2

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 470 g (5.00 mol), 4,4'-BMMB 233.44 g (0.96 mol), and 42% fumarin aqueous solution 45.71 g were fed. (0.64 mol), 0.26 g of a 50% aqueous sulfuric acid solution, and reacted at 100 ° C for 3 hours.

Thereafter, the reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 360 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 70 mPa‧s, and the OH equivalent by the acetonitrile method was 164 g/eq.

Synthesis Example 3

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 470 g (5.00 mol), 4.4'-BMMB 288.10 g (1.19 mol), and 42% fumarin aqueous solution 56.43 g (0.79) were fed. Mohr), 0.29 g of a 50% aqueous sulfuric acid solution, was reacted at 100 ° C for 3 hours.

Thereafter, the reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 450 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 75 mPa‧s, and the OH equivalent by the acetonitrile method was 171 g/eq.

Synthesis Example 4

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen introduction tube, 404.2 g (4.30 mol) and 4,4'-bis(chloromethyl)biphenyl (hereinafter referred to as 4, 4') were fed. - BCMB) 150.7 g (0.60 mol), reacted at 100 ° C for 3 hours, then added 28.57 g (0.40 mol) of a 42% aqueous solution of formalin, and reacted at 100 ° C for 3 hours. In the meantime, the produced hydrochloric acid was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 251 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 40 mPa‧s, and the OH equivalent by the acetonitrile method was 166 g/eq.

Synthesis Example 5

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen introduction tube, 470 g (5.00 mol) of phenol, 302.5 g (1.25 mol) of 4.4'-BMMB, and 0.28 g of a 50% aqueous sulfuric acid solution were fed while maintaining The reaction was allowed to proceed for 2 hours while the temperature was raised at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 380 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 115 mPa‧s, and the OH equivalent by the acetonitrile method was 202 g/eq.

Synthesis Example 6

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 470 g (5.00 mol) of phenol, 389.1 g (1.61 mol) of 4,4'-BMMB, and 0.28 g of a 50% aqueous sulfuric acid solution were fed. The reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 470 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 130 mPa‧s, and the OH equivalent by the acetonitrile method was 208 g/eq.

Synthesis Example 7

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 274.5 g (2.92 mol), 4,4'-BMMB 290.4 g (1.23 mol), and 42% fumarin aqueous solution 57.14 were fed. g (0.82 mol), 0.22 g of a 50% aqueous sulfuric acid solution, and reacted at 100 ° C for 3 hours.

Thereafter, the reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 370 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 90 mPa‧s, and the OH equivalent by the acetonitrile method was 188 g/eq.

Synthesis Example 8

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 685 g (7.27 mol), 4,4'-BMMB 151.15 g (0.62 mol), and 42% fumarin aqueous solution 29.7 g were fed. (0.4 mol), 0.34 g of a 50% aqueous sulfuric acid solution, and reacted at 100 ° C for 3 hours.

Thereafter, the reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 250 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition was 40 mPa‧s, and the OH equivalent by the acetonitrile method was 164 g/eq.

Synthesis Example 9

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 141 g (1.5 mol) of phenol, 248.6 g (1.03 mol) of 4,4'-BMMB, and 0.16 g of a 50% aqueous sulfuric acid solution were fed. The reaction was allowed to proceed for 2 hours while maintaining the reaction temperature at 125 ° C, and then the temperature was raised to 165 ° C for 3 hours. In the meantime, the produced methanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled, and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 280 g of a phenol resin composition.

The ICI viscosity of the obtained phenol resin composition could not be measured at 150 ° C, and the OH equivalent by the acetonitrile method was 240 g / eq.

The synthesis conditions and physical property values of the phenol resin compositions obtained in Synthesis Examples 1 to 9 are shown in Table 1. Meanwhile, the content (%) of the compound of the formula (5-1) and (5-2) in the phenol resin composition is a phenol resin obtained by the above-described method for measuring the number average molecular weight (that is, the additive is removed). The ratio of the peak areas of the compounds of the general formulae (5-1) and (5-2) in the full peak area was determined.

Synthesis Example 10

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen introduction tube, 470.00 g (5.00 mol) and 1,4-bis(methoxymethyl)benzene (hereinafter referred to as 1,4-) were fed. PXDM) 276.67 g (1.67 mol), 0.33 g of a 50% aqueous sulfuric acid solution, and reacted at 130 ° C for 1 hour.

Thereafter, the reaction temperature was raised to 160 ° C, and the reaction was carried out for 3 hours. In the meantime, the produced methanol was distilled off. Thereafter, it was cooled to 80 ° C, and 83.44 g (1.17 mol) of a 42% formalin aqueous solution was added dropwise. After the dropwise addition, the temperature was raised to 100 ° C, and the reaction was carried out for 1 hour. After the reaction was completed, the water was washed three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 430 g of a phenol resin composition.

[Manufacture of epoxy resin composition]

The epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were synthesized using the phenol resin compositions obtained in Synthesis Examples 1 to 10. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the epoxy resin composition were measured by the following methods.

Using a gel permeation chromatography (HCL-8220 (manufactured by TOSHO Co., Ltd.)), the result of measuring the standard substance under the following conditions was used as a calibration curve, and the number average molecular weight (Mn) of each resin composition converted into polystyrene was determined. And weight average molecular weight (Mw).

Use the following columns in series:

TSK-GEL H type

G2000H×L 4 branches

G3000H×L 1 branch

G4000H×L 1 branch

Column pressure; 13.5MPa

Solution: tetrahydrofuran (THF)

Flow rate: 1ml/min

Measuring temperature: 40 ° C

Detector: Spectrophotometer (UV-8020)

Range: 2.56 wavelength 254nm and RI

Further, the content % of the compound (dinuclear compound) of the general formulae (3-1) and (3-2) in the epoxy resin composition is an epoxy resin obtained by the above-described method for measuring the number average molecular weight (i.e., The ratio of the peak areas of the compounds of the general formulae (3-1) and (3-2) in the total peak area of the additive was determined.

Example 1

The phenol resin composition obtained in Synthesis Example 1 was fed with 298.8 g (1.80 mol), epichlorohydrin 999.0 g (10.80 mol), and methanol in a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube. 93.75g, so that it dissolves evenly. 75 g of solid 96% sodium hydroxide (1.80 mol) was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

480 g of methyl isobutyl ketone was added to dissolve the residue in the pot. A solution of 28.80 g (0.18 mol) of a 25% aqueous sodium hydroxide solution was added at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated 5 times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 382 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity at 150 ° C of 34 mPa ‧ and an epoxy equivalent of 233 g / eq. The Mn and Mw of the obtained epoxy resin composition were 682 and 835, respectively.

Example 2

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 278.8 g (1.70 mol) of phenol resin composition obtained in Synthesis Example 2, 943.5 g (10.20 mol) of epichlorohydrin, and methanol were fed. 88.54g, so that it dissolves evenly. A solid 96% sodium hydroxide 70.83 g (1.70 mole) was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

450 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 27.20 g (0.17 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated 5 times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 364 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity of 56 mPa ‧ at 150 ° C and an epoxy equivalent of 239 g / eq. The Mn and Mw of the obtained epoxy resin composition were 775 and 1017, respectively.

Example 3

In a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 290.7 g (1.70 mol) of phenol resin composition obtained in Synthesis Example 3, 943.5 g (10.20 mol) of epichlorohydrin, and methanol were fed. 88.54g, so that it dissolves evenly. A solid 96% sodium hydroxide 70.83 g (1.70 mole) was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

450 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 27.20 g (0.17 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 380 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity at 150 ° C of 64 mPa ‧ and an epoxy equivalent of 244 g / eq. The Mn and Mw of the obtained epoxy resin composition were 873 and 1274, respectively.

Example 4

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 232.4 g (1.40 mol) of phenol resin composition obtained in Synthesis Example 4, 777.0 g (8.40 mol) of epichlorohydrin, and methanol were fed. 72.92g, so that it dissolves evenly. 58.33 g (1.40 mol) of solid 96% sodium hydroxide was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

373 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 22.40 g (0.14 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 290 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity of 33 mPa ‧ at 150 ° C and an epoxy equivalent of 233 g / eq.

Example 5

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 282 g (1.5 mol) of phenol resin composition obtained in Synthesis Example 7, 832.5 g (9.0 mol) of epichlorohydrin, and methanol 78.13 were fed. g, so that it dissolves evenly. 62.5 g (1.5 mol) of solid 96% sodium hydroxide was added in batches at 50 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

500 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 24.0 g (0.1 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 340 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity at 150 ° C of 82 mPa ‧ and an epoxy equivalent of 250 g / eq.

Example 6

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 272 g (2.0 mol) of phenol resin composition obtained in Synthesis Example 10, 1110 g (12.0 mol) of epichlorohydrin, and 88.00 g of methanol were fed. So that it dissolves evenly. The solid 96% sodium hydroxide 83.33 g (2.0 mol) was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

480 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 32.0 g (0.2 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated 5 times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 340 g of an epoxy resin composition.

Comparative example 1

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 303.0 g (1.50 mol) of phenol resin composition obtained in Synthesis Example 5, 832.5 g (9.0 mol) of epichlorohydrin, and methanol were fed. 78.13g, so that it dissolves evenly. 62.50 g (1.50 mol) of solid 96% sodium hydroxide was added in batches at 50 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

460 g of methyl isobutyl ketone was added to dissolve the residue in the pot. A solution of 24.00 g (0.15 mol) of a 25% aqueous sodium hydroxide solution was added at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 380 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity at 150 ° C of 100 mPa ‧ and an epoxy equivalent of 273 g / eq. The Mn and Mw of the obtained epoxy resin composition were 732 and 940, respectively.

Comparative example 2

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 312.0 g (1.50 mol) of phenol resin composition obtained in Synthesis Example 6, 832.5 g (9.0 mol) of epichlorohydrin, and methanol were fed. 78.13g, so that it dissolves evenly. 62.50 g (1.50 mol) of solid 96% sodium hydroxide was added in batches at 50 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

460 g of methyl isobutyl ketone was added to dissolve the residue in the pot. A solution of 24.00 g (0.15 mol) of a 25% aqueous sodium hydroxide solution was added at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 380 g of an epoxy resin composition.

The obtained epoxy resin composition had an ICI viscosity at 150 ° C of 103 mPa ‧ and an epoxy equivalent of 276 g / eq. The Mn and Mw of the obtained epoxy resin composition were 822 and 1152, respectively.

Comparative example 3

As the epoxy resin, an epoxy resin (EOCN-1020-55: manufactured by Nippon Kayaku Co., Ltd.) obtained by epoxidizing a commercially available phenol resin synthesized from o-cresol and fumarin is used.

Comparative example 4

The phenol resin composition obtained in Synthesis Example 8 was fed with 278.8 g (1.70 mol), epichlorohydrin 943.5 g (10.20 mol), and methanol in a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube. 88.54g, so that it dissolves evenly. A solid 96% sodium hydroxide 70.83 g (1.70 mole) was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

450 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 27.20 g (0.17 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 360 g of an epoxy resin composition.

The resulting epoxy resin composition had an ICI viscosity at 150 ° C of 30 mPa ‧ and an epoxy equivalent of 230 g / eq.

Comparative Example 5

Into a glass reaction vessel equipped with a stirring device, a condenser, and a nitrogen gas introduction tube, 240 g (1.0 mol) of phenol resin composition obtained in Synthesis Example 9, 555 g (6.0 mol) of epichlorohydrin, and 78.13 g of methanol were fed. So that it dissolves evenly. 41.7 g (1.0 mol) of solid 96% sodium hydroxide was added in portions at 90 ° C for 90 minutes. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and after the temperature was raised to 70 ° C, the reaction was continued for 2 hours. After the reaction was completed, excess epichlorohydrin was removed under reduced pressure.

500 g of methyl isobutyl ketone was added to dissolve the residue in the pot. 16.0 g (0.1 mol) of a 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C for 1 hour. After the completion of the reaction, the water washing treatment was repeated five times until the water layer became neutral. Methyl isobutyl ketone was distilled off under heating under reduced pressure to obtain 300 g of an epoxy resin composition.

The ICI viscosity at 150 ° C of the obtained epoxy resin composition could not be measured, and the epoxy equivalent was 320 g/eq.

The physical property values of the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, and the blending ratio of the cured product 1 of the epoxy resin composition obtained by the method shown below and the characteristics of the cured product 1 The finishing is shown in Table 2.

[Modification of hardened material 1]

Using the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, and a phenolic phenolic resin of HF-3M (hydroxyl equivalent weight: 107 g/eq) manufactured by Minghe Chemical Co., Ltd. as a curing agent, as a hardening accelerator Triphenylphosphine (also referred to as TPP).

Specifically, the epoxy resin composition and the hardener are blended in such a manner that the ratio of the phenolic hydroxyl equivalent to the epoxy equivalent is 1:1, and the feed is 0.15% by weight based on the weight of the blended epoxy resin composition. TPP catalyst. These were heated to 150 ° C, melt-mixed, vacuum-deaerated, and molded in a 150 ° C stamper (thickness: 4 mm), and cured at 150 ° C for 5 hours, and then cured at 180 ° C for 8 hours to prepare a molded body.

The test method of various physical properties of the obtained molded body (hardened product) is as described above.

[Modification of hardened material 2]

The physical property values of the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, and the blending ratio of the cured product 2 of the epoxy resin composition obtained by the method shown below, and the characteristics of the cured product 2, The finishing is shown in Table 3.

Using the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, HF-3M (hydroxyl equivalent: 107 g/eq) of a general-purpose phenol phenol resin manufactured by Minghe Chemical Co., Ltd. as a curing agent, as a hardening accelerator Triphenylphosphine (also referred to as TPP) and cerium oxide (MSR-2212) manufactured by Ronson Corporation as a filler were synthesized by the following method (Epoxy Moldering Compound).

The epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 and the above-mentioned hardener were blended in such a manner that the ratio of the phenolic hydroxyl equivalent to the epoxy equivalent was 1:1, and the epoxy resin was fed in relation to the blended epoxy resin. The composition had a weight of 2.3 wt% of TPP catalyst. The filler was added thereto in such a manner as to be 83% by weight, and the EMC powder was adjusted by kneading in a biaxial kneader under conditions of 100 to 110 ° C and pulverizing.

The obtained EMC powder was used as a tablet to perform spiral flow measurement.

Further, a test piece was prepared by using the above-mentioned EMC powder by a transfer molding machine, and after hardening at 180 ° C for 8 hours, a test piece for water absorption, strength, and flame retardancy evaluation was obtained.

In Tables 2 and 3 above, "%/EP" indicates the weight % relative to the epoxy resin composition.

In Tables 2 and 3 above, the ICI viscosity at 150 ° C of Comparative Example 5 was such that the viscosity of each resin composition was too high to be measured.

It is apparent that the epoxy resin composition obtained in the examples of the present invention is an epoxy resin which maintains high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, rapid hardening, and flame retardancy and has low melt viscosity. Composition.

[Industrial availability]

According to the present invention, an epoxy resin composition in which a cured product maintains a high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid hardening, and flame retardancy and has a low melt viscosity can be provided.

Claims (8)

An epoxy resin composition containing a component of the following formula (1), and a content ratio of a compound represented by the following formulas (3-1) and (3-2) is 50% or less, and at 150 ° C The melt viscosity is above 5mPa‧s, less than 100mPa‧s, In the formula, R represents a crosslinking group selected from at least one of a biphenyl group and a benzoyl group represented by the following general formulae (2-1) and (2-2), and R ¹ and R ² and R ³ may be the same or different, and is an alkyl group having 1 to 6 carbon atoms or an aryl group, and p, q, and r are each an integer of 0 to 2; further, m and n are positive numbers, and G represents glycidol. base, In the formula, G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. The epoxy resin composition of claim 1, wherein m/n is from 0.04 to 20. The epoxy resin composition of claim 1 or 2, wherein R contains at least a stretched phenyl crosslinker. The epoxy resin composition of claim 3, wherein the extended biphenyl crosslinking group contains a 4,4'-extended biphenyl crosslinking group. An epoxy resin composition according to claim 1 or 2, which further comprises a hardener and a hardening accelerator as required. A cured product obtained by hardening an epoxy resin composition according to any one of claims 1 to 5. A method for producing an epoxy resin composition, which is an epoxy resin composition according to any one of claims 1 to 4, which is characterized in that a phenol resin composition and an epihalohydrin are used in an alkali metal hydrogen In the presence of an oxide, the phenol resin composition contains a component of the following formula (4), and the content ratio of the compound represented by the following formulas (5-1) and (5-2) is 50% or less. , In the formula, R represents a crosslinking group selected from at least one of a biphenyl group and a benzoyl group represented by the following general formulae (2-1) and (2-2), and R ¹ and R ² and R ³ may be the same or different, each is an alkyl group having 1 to 6 carbon atoms, or an aryl group, and p, q, and r are each an integer of 0 to 2; further, m and n are positive numbers, In the formula, R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. The method for producing an epoxy resin composition according to claim 7, wherein the phenol resin composition is a phenol compound, formaldehyde, and a compound selected from the group consisting of the following formulae (6-1) and (6-2) Reaction of one or more crosslinkers of a compound: Here, in the formula, Y represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.