KR101410919B1 - Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof - Google Patents

Abstract

The present invention provides an epoxy resin, a polyhydric hydroxy resin, and a composition thereof, which are excellent in flame retardance, moisture resistance, low elasticity, and the like, and are suitable for use in encapsulation of electronic components, circuit board materials and the like.
Is obtained by reacting 0.3 to 1.0 mol of styrene with 1 mol of phenol novolak as a polyhydric hydroxy compound in the presence of an acid catalyst, and the area% when the monohydric hydroxy compound is detected by gel permeation chromatography as a byproduct % Or less of styrene-modified polyhydric hydroxy resin. Further, it is an epoxy resin obtained by reacting styrene-modified polyhydric hydroxy resin with epichlorohydrin, and further an epoxy resin composition containing this styrene-modified polyhydric hydroxy resin or epoxy resin as an essential component.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyhydroxy resin, an epoxy resin, a process for producing the same, an epoxy resin composition, and a cured product thereof. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an epoxy resin which is excellent in curability and at the same time gives a cured product excellent in flame retardancy, moisture resistance and low elasticity, a polyhydric hydroxy resin suitable as an intermediate thereof, a method for producing them, an epoxy resin composition using the epoxy resin composition and a cured product thereof, An insulating material for electrical and electronic fields such as a sealing material, a printed wiring board and the like.

Epoxy resins have been widely used for industrial purposes, but their required performance has recently been advanced. For example, there is a semiconductor encapsulating material as a representative example of a resin composition having an epoxy resin as a main agent. As the degree of integration of semiconductor elements is improved, the package size becomes larger and thinner, And it is desired to develop a material having excellent solder heat resistance. Therefore, the encapsulating material is required to have a low moisture absorption and an improvement in adhesiveness and adhesion at an interface between different materials such as a lead frame and a chip. From the viewpoint of improving solder heat resistance, it is desired to develop a material having a low dielectric constant in view of the reduction of dielectric loss as well as the improvement of low hygroscopicity, high heat resistance and high adhesion in circuit board materials. In order to meet these demands, various novel epoxy resins and curing agents have been studied. In recent years, there has been a desire to exclude halogen-based flame retardants from the viewpoint of environmental load reduction, and epoxy resins and curing agents having better flame retardancy are required.

Therefore, various epoxy resins and epoxy resin curing agents have been studied due to the above background. As an example of an epoxy resin curing agent, a naphthalene-based resin is known. Patent Document 1 discloses application of a naphthol aralkyl resin to a semiconductor encapsulant, and it is described that it is excellent in flame retardance, low hygroscopicity, and low thermal expansion. In Patent Document 2, a curing agent having a biphenyl structure has been proposed and is said to be effective for improving flame retardancy. However, both the naphthol aralkyl resin and the biphenyl aralkyl resin have a drawback of poor curability, and the flame retardancy improving effect is not sufficient in some cases.

On the other hand, it is not known yet to meet these requirements for epoxy resins. For example, a known bisphenol-type epoxy resin is widely used because it is in a liquid state at room temperature and has excellent workability and easy mixing with a curing agent, an additive, etc. However, it has a problem in heat resistance and moisture resistance. An o-cresol novolac epoxy resin is known as an improved heat resistance, but its flame retardancy is insufficient.

As a countermeasure for improving the flame retardancy without using a halogen-based flame retardant, a method of adding a phosphate ester flame retardant is disclosed. However, the method using a phosphate ester flame retardant is not sufficient in moisture resistance. Further, under a high temperature and high humidity environment, the phosphoric acid ester is hydrolyzed to lower the reliability as an insulating material.

Patent documents 2 and 3 disclose examples in which an aralkyl type epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant to improve flame retardancy without containing a phosphorus atom or a halogen atom. Patent Document 4 discloses an example of using an aralkyl type epoxy resin having a naphthalene structure. However, these epoxy resins do not have sufficient performance in either flame retardance, moisture resistance or heat resistance.

On the other hand, Patent Reference 5 discloses benzylated polyphenols and epoxy resins as examples of improving heat resistance, moisture resistance, and resistance to cracking, but they are not focused on flame retardancy. They are resins obtained by using phenol novolak as a starting material and then addition reaction of benzyl chloride. Since the reaction is carried out under strongly acidic conditions in which hydrochloric acid generated in the reaction is utilized as a catalyst, methylene bridges of phenol novolak are partially cleaved Thereby causing phenol to be a by-product. That is, there is a problem that the curing property and the heat resistance are lowered by containing a monofunctional phenol compound as a by-product.

Patent Document 6 discloses a method of reacting phenol novolak and styrene in the presence of an acid catalyst as an example of a method for producing styrene-modified novolak. However, since sulfuric acid catalysts which are strongly acidic at high temperature are used, There is a problem that the methylene crosslinking of the novolac is partially cleaved and phenol is produced as a by-product.

On the other hand, as an example of the epoxy resin composition focused on improvement in moisture resistance and low stress, an epoxy resin composition using a styrenated phenol novolac resin and an epoxy resin is disclosed in Patent Documents 7 and 8, It is not the flame retardancy. In addition, since they are produced by using styrenated phenol as a starting material and then converting them into novolac, there is a problem that the styrenated phenol remains in the resin to lower the hardenability and the heat resistance.

Japanese Patent Application Laid-Open No. 2005-344081 Japanese Patent Application Laid-Open No. 11-140166 Japanese Patent Application Laid-Open No. 2000-129092 Japanese Patent Application Laid-Open No. 2004-59792 Japanese Patent Application Laid-Open No. 8-120039 Japanese Patent Application Laid-Open No. 48-52895 Japanese Patent Application Laid-Open No. 5-132544 Japanese Patent Application Laid-Open No. 5-140265

It is an object of the present invention to provide an epoxy resin which is excellent in curability and excellent in flame retardance, moisture resistance and low elasticity in applications such as lamination, molding, casting and adhesion, , An object of the present invention is to provide an epoxy resin composition which is useful for encapsulation of electrical and electronic parts and circuit board materials which give excellent cured products such as low elasticity and the like and a cured product thereof.

That is, the present invention relates to a polyhydric hydroxy resin represented by the following general formula (1), wherein the area when the monohydric hydroxy compound represented by the following general formula (2) is detected by gel permeation chromatography (GPC; RI) % ≪ / RTI > of the polyhydric hydroxy resin.

(Wherein R ₁ represents hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, R ₂ represents a substituent represented by the following formula (a), and n represents a number of 0 to 20. p represents a number of 0.1 to 2.5. And R ₃ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

(Wherein p represents a number of 0 to 3, and R ₁ and R ₃ represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)

The present invention also provides a process for producing a polyhydroxy compound, which comprises reacting 0.1 to 1.0 mole of styrene with 1 mole of a hydroxyl group of the polyhydric hydroxy compound represented by the following general formula (3) at a reaction temperature of 40 to 120 占 폚 in the presence of 10 to 400 ppm by weight , And the substituent represented by the formula (a) is substituted with a benzene ring of a polyhydric hydroxy compound.

The present invention also relates to an epoxy resin represented by the following general formula (4), wherein the unit price epoxy resin represented by the following general formula (5) is detected by gel permeation chromatography (GPC; RI) Or less.

(Wherein G represents a glycidyl group, R ₁ represents hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, R ₂ represents a substituent represented by the above formula (a) and R ₃ represents hydrogen or a group of 1 to 6 carbon atoms Hydrocarbon group, n represents a number of 1 to 20, and p represents a number of 0.1 to 2.5.

(Wherein G represents a glycidyl group, R ₁ and R ₃ represent hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, and p represents a number of 0 to 3.)

The present invention also relates to a process for producing an epoxy resin, which comprises reacting the above polyhydric hydroxy resin with epichlorohydrin.

The present invention also relates to an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition comprises one or both of the polyhydric hydroxy resin and the epoxy resin as essential components. The present invention also relates to an epoxy resin cured product obtained by curing the above epoxy resin composition.

According to the present invention, it is possible to provide an epoxy resin, a polyhydric hydroxy resin, and a composition thereof, which are excellent in flame retardancy, humidity resistance, low elasticity, and the like, and are suitable for sealing of electronic parts and materials for circuit boards.

1 is a GPC chart of the polyhydric hydroxy resin obtained in the examples.
2 is a GPC chart of the polyhydric hydroxy resin obtained in Synthesis Example.
3 is a GPC chart of the epoxy resin obtained in the examples.
4 is a GPC chart of the epoxy resin obtained in Synthesis Example.

First, the polyhydric hydroxy resin (hereinafter abbreviated as STPN) of the present invention will be described. StPN of the present invention is represented by the general formula (1), which can be obtained by reacting a polyhydric hydroxy compound (also referred to as polyhydric hydroxy compound (3)) represented by the general formula (3) with styrene.

As a method for adding the styrene to the polyhydric hydroxy compound, the reaction is generally carried out at a high temperature of 120 to 170 DEG C in the presence of an acid catalyst such as hydrochloric acid. However, when the reaction is carried out at a high temperature in the presence of an acid catalyst, there is a problem in that a monohydric phenol is produced as a by-product accompanied by cleavage of a methylene bond as a linking moiety of the polyhydric hydroxy compound. To suppress such side reactions, the reaction temperature is lowered in the range of 40 to 120 占 폚, and the by-product of the unit phenol compound can be reduced by reducing the catalytic amount in the range of 10 to 400 ppm. That is, when the resultant polyhydric hydroxy resin is used as a curing agent for an epoxy resin, excellent physical properties such as curability and heat resistance are exhibited.

The content of the monohydric hydroxy compound (also referred to as the monohydric hydroxy compound (2)) represented by the above general formula (2) in the polyhydric hydroxy resin component produced by the side reaction is detected by gel permeation chromatography (GPC; RI) Is preferably not more than 3% in terms of area% when it is used. When the amount is larger than the above range, the monohydric hydroxy compound contained as a by-product tends to lower the curability when a polyhydric hydroxy resin is used as the epoxy resin curing agent. In addition, since the monohydric hydroxy compound lowers the crosslinking density even in the epoxy resin cured product, the heat resistance tends to deteriorate.

As a by-product contained in the polyhydric hydroxy resin, a styrene oligomer can be mentioned as a component other than the monohydric hydroxy compound. This is a by-product produced by the polymerization reaction of styrene itself, and in particular includes styrene dimer as a low molecular weight component. This styrene dimer component also tends to lower the curability and heat resistance as the monohydric hydroxy compound.

In addition, in the epoxy resin cured product, the hydroxypropyl group produced by the reaction of the epoxy group and the hydroxyl group is liable to be burned. However, by adding the styrene group to the polyhydric hydroxy compound to increase the hydroxyl group equivalent, an inflammable component ) Is lowered, so that a high flame retardancy can be exhibited. Further, the aromaticity of the polyhydric hydroxy resin is further improved by the addition of the styrene which is rich in aromatics, and the flame retardancy and the moisture resistance are also effectively improved.

Therefore, a highly flame-retardant epoxy resin composition, particularly an epoxy resin composition for semiconductor encapsulation, can be obtained by using them. In other words, excellent curability of the compositions and excellent physical properties such as high flame retardance, moisture resistance, and low elasticity are exhibited, and thus it is possible to obtain highly reliable electronic / electronic parts encapsulation, circuit board materials and the like.

The StPN of the present invention is obtained by subjecting the styrene to an addition reaction with the polyhydric hydroxy compound (3) represented by the general formula (3). In consideration of the balance between the flame retardancy and curability of the resulting cured product, the ratio of the polyhydric hydroxy compound (3) to the styrene compound is preferably in the range of 0.1 to 2.5 moles in terms of the ratio of styrene to 1 mole of the polyhydric hydroxy compound More preferably 0.1 to 1.0 mole, and still more preferably 0.3 to 0.8 mole. When the amount is less than this range, the properties of the polyhydric hydroxy compound as the raw material remain unchanged. When the amount is larger than the above range, the functional group density becomes too low and the curability tends to be lowered.

In this reaction, the styrenes are substituted with a styrenyl group represented by the formula (a) in addition to an aromatic ring having an OH group in the polyhydroxy compound (3). The position of addition of the styrenes is an ortho and / or para position which is a vacant position of the polyhydric hydroxy compound, and is mainly a para position.

The melt viscosity of the StPN of the present invention at 150 캜 is preferably in the range of 0.01 to 10.0 Pa · s. From the viewpoint of workability, the lower the melt viscosity in the above range, the more preferable.

Further, the softening point is preferably 40 to 150 ° C, and more preferably 50 to 100 ° C. Here, the softening point refers to the softening point measured based on the ring method (JIS-K-2207) of JIS-K-2207. When it is lower than this, the heat resistance of the cured product is lowered when it is blended with the epoxy resin, and when it is higher than that, the fluidity at the time of molding is lowered.

R ₂ represents a styrenyl group represented by the above formula (a). p represents a number of 0.1 to 2.5, which means the average number (number average) of styryl groups substituted in one phenolic ring. p is preferably 0.1 to 2, 0.1 to 1.0 mole, 0.3 to 1, and 0.3 to 0.8 mole in this order. On the other hand, up to four styrenyl groups can be substituted in the phenol ring at both ends, and up to three styrenyl groups can be substituted in the middle phenol ring, so that when n is 1, up to 8 styrenyl groups can be substituted.

In another aspect, the StPN of the present invention preferably has a number of substitution (number average) of styryl groups per molecule of 1 or more, more preferably 2 or more, still more preferably 2.6 to 4.

In formula (a), R ₃ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen. This R ₃ is determined by styrenes used as a reaction raw material.

In the general formula (1), n represents a number of 1 to 20, preferably an average of 1.5 to 5.0.

Next, a method for producing StPN of the present invention will be described. As the polyhydric hydroxy compound (3) used in the method for producing StPN of the present invention, phenol novolak is used.

The phenols used for obtaining the polyhydric hydroxy compound (3) are phenol or a hydrocarbon-substituted phenol having 1 to 6 carbon atoms. Examples of the hydrocarbon-substituted phenol include cresols, ethyl phenols, isopropyl phenols, tert- Phenols, phenyl phenols, and the like. Preferably phenol or an alkyl-substituted phenol having 1 to 3 carbon atoms, and more preferably phenol.

These phenols may contain small amounts of other phenolic components. For example, when phenol is used as the phenol, other phenol components include o-cresol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, tertiary butyl phenol, allyl phenol, Naphthalene diol, 1,7-naphthalene diol, 2-naphthalene diol, 2-naphthalene diol, 2-naphthalene diol, , 6-naphthalene diol, 2,7-naphthalene diol, and the like. These phenols or naphthols may include two or more kinds.

The styrene used for the reaction with the polyhydric hydroxy compound is styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms. These styrenes may contain small amounts of other reaction components. When an unsaturated bond-containing component such as? -Methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole or vinylnaphthalene is contained as another reaction component, the resultant polyhydric hydroxy resin has a group And the like. The phenol resin obtained by the process for producing a polyhydric hydroxy resin of the present invention may contain a polyhydric hydroxy resin having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention may include an epoxy resin having such a substituent.

This reaction can be carried out in the presence of an acid catalyst, and the amount of the catalyst is used in the range of 10 to 400 ppm, preferably in the range of 100 to 350 ppm. If it is larger than the above range, the methylene crosslinking of the phenol novolac tends to be cleaved, and the curing property and the heat resistance are lowered by the monohydric phenol component produced as a by-product of the cleavage reaction. On the other hand, if it is less than this range, the reactivity is lowered, and a large amount of unreacted styrene monomer remains. The term "catalytic amount" as used herein means the amount of the catalyst relative to the total weight of the polyhydric hydroxy compound and styrene used in the reaction.

This reaction can be carried out in the presence of an acid catalyst. The acid catalyst may be appropriately selected from well-known inorganic acids and organic acids. For example, a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid or an organic acid such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid or diethylsulfuric acid, or an organic acid such as zinc chloride, Lewis acid or ion exchange resin of activated carbon, solid clay such as activated clay, silica-alumina, zeolite and the like.

The reaction temperature in this reaction is in the range of 40 to 120 ° C. If it is lower than the above range, the reactivity decreases and the reaction time becomes longer. In addition, when it is higher than the above range, the methylene crosslinking of phenol novolak tends to be partially cleaved, and curing property and heat resistance are lowered due to a monohydric phenol component produced as a by-product of the cleavage reaction.

This reaction is usually carried out for 1 to 20 hours. The reaction may be carried out in the presence of an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve, a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone, , Ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent.

As a specific method for carrying out this reaction, a method is generally used in which all the raw materials are charged at a constant temperature and reacted at a predetermined temperature, or a styrenic compound is dropped while charging the polyhydric hydroxy compound and the catalyst at a predetermined temperature . In this case, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. After the reaction, if a solvent is used, the catalyst component is removed, if necessary, and the solvent is distilled off to obtain the resin of the present invention. When the solvent is not used, the desired product can be obtained by directly discharging have.

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

The epoxy resin (abbreviated as StPNE) of the present invention is represented by the general formula (4). The polyhydric hydroxy resin (StPN) is represented by the general formula (1). StPNE can be obtained by epoxidizing StPN.

In the general formula (4), the symbols common to the general formula (1) have the same meaning. G represents a glycidyl group, which is formed by the reaction of the hydroxyl group of the general formula (1). R ₁ is a styryl group.

The StPNE of the present invention is advantageously produced by reacting StPN represented by the above general formula (1) with epichlorohydrin, but is not limited to this reaction. However, StPN does not contain more than 3% of the above monovalent hydroxy compound. Therefore, the unit price epoxy resin (also referred to as the unit epoxy resin (5)) represented by the above general formula (5) can be made to 3% or less.

In addition to the reaction of StPN with epichlorohydrin, a method of reacting StPN with allyl halide to give an allyl ether compound followed by reaction with peroxide may be selected. The reaction of the StPN with epichlorohydrin can be carried out in the same manner as in the conventional epoxidation reaction.

For example, by dissolving the above StPN in excess of epichlorohydrin and then reacting in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 20 to 150 ° C, preferably 30 to 80 ° C for 1 to 10 hours . The amount of the alkali metal hydroxide to be used at this time is in the range of 0.8 to 1.5 moles, preferably 0.9 to 1.2 moles per 1 mole of the hydroxyl group of StPN. Epichlorohydrin is used in excess of 1 mol of hydroxyl groups in StPN, and is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, per mol of hydroxyl group in StPN. After completion of the reaction, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired epoxy A resin can be obtained.

The epoxy resin composition of the present invention comprises at least an epoxy resin and a curing agent.

1) A composition containing StPNE as a part or all of an epoxy resin.

2) a composition containing StPN as a part or all of a curing agent.

3) A composition comprising SPE and StPN as a part or all of an epoxy resin and a curing agent.

In the case of the compositions 2) and 3), StPN is included as an essential ingredient. The blending amount of StPN is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. When the amount is less than the above range, the effect of improving the flame retardancy and moisture resistance is small, and if it is more than this range, the moldability and the strength of the cured product are deteriorated.

When StPN is used as the total amount of the curing agent, the amount of StPN to be blended is generally calculated in consideration of the OH group of StPN and the equivalence balance of the epoxy groups in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. The hardening property of the epoxy resin composition is lowered, and the heat resistance and mechanical strength of the cured product are lowered.

As the curing agent, a curing agent other than StPN can be used in combination. The blending amount of the other curing agent is determined within a range in which the blending amount of StPN is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight based on 100 parts by weight of the epoxy resin. When the blending amount of StPN is less than this range, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small, and if it is more than this range, moldability and strength of the cured product are deteriorated. In this case, the equivalent ratio of the epoxy resin to the curing agent (total) is in the above range.

As the curing agent other than StPN, any known epoxy resin curing agent can be used, and examples thereof include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines, and the like. Among these, in the field where high electrical insulation property such as a semiconductor encapsulant is required, it is preferable to use a polyhydric phenol as a curing agent. Specific examples of the curing agent are shown below.

Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride, anhydrous dodecylsuccinic acid, anhydrous nadic acid, anhydrous trimellitic anhydride And so on.

Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin and naphthalenediol; (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolac, naphthol novolac, Representative trivalent or higher phenols are available. Further, it is preferable to use a divalent phenol such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'- biphenol, hydroquinone, resorcin, , Polyhydric phenolic compounds synthesized by condensation agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, and bischloromethylnaphthalene.

Examples of the amines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine. Aliphatic amines such as aromatic amines, ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

One or more of these curing agents may be used in the composition.

The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, Tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalene diols, and other divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, and o-cresol novolac, epoxides of cocondensation resins of dicyclopentadiene and phenols, phenols and paraxylylene dichloride , Epoxides of biphenyl aralkyl type phenol resins synthesized from phenols and bischloromethyl biphenyl, naphthol aralkyl resins synthesized from naphthols and para-xylylene di-chlorides, etc. And the like. These epoxy resins may be used alone or in combination of two or more.

For the above 1) and 3) compositions, StPNE is included as an essential ingredient. In this epoxy resin composition, a different kind of epoxy resin may be blended in addition to StPNE as an epoxy resin component. As the epoxy resin in this case, any conventional epoxy resin having two or more epoxy groups in the molecule can be used. For example, divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone and resorcin, and tris- (4-hydroxyphenyl) Methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, and o-cresol novolak, phenolic aralkyl resins, biphenyl aralkyl resins , Naphthol-based aralkyl resins, or glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins may be used alone or in combination of two or more. In the case of a composition comprising StPNE as an essential component of the present invention, the blending amount of StPNE is preferably in the range of 5 to 100%, more preferably 60 to 100% of the total epoxy resin.

To the epoxy resin composition of the present invention, an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene · coumarone resin or phenoxy resin is suitably compounded You can. The addition amount is usually in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention may further contain additives such as an inorganic filler, a pigment, a flame retardant, a thixotropy-imparting agent, a coupling agent, and a fluidity-improving agent. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina and the like . When it is used in a semiconductor encapsulant, a preferable amount is 70% by weight or more, and more preferably 80% by weight or more.

Examples of pigments include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include a silicone type, a castor oil type, an aliphatic amide wax, an oxidized polyethylene wax, and an organic bentonite type.

In the epoxy resin composition of the present invention, a curing accelerator may be used if necessary. Examples thereof include amines, imidazoles, organic phosphines and Lewis acids. Specific examples thereof include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanol Amine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; a tertiary amine such as 2-methylimidazole, 2-phenylimidazole, Imidazoles such as methylimidazole and 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine, and organic phosphines such as tetraphenyl Tetra-substituted phosphonium tetra-substituted borates such as tetrabutylphosphonium tetrabutylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate and the like, 2-ethyl-4-methylimidazole tetraphenylborate , Tetramhenylboron salts such as N-methylmorpholine-tetraphenylborate . The addition amount is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

If necessary, the resin composition of the present invention may contain a releasing agent such as carnauba wax and OP wax, a coupling agent such as? -Glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, antimony trioxide Flame retardants such as silicone oil, lubricants such as calcium stearate, and the like can be used.

The epoxy resin composition of the present invention can be obtained by impregnating a fibrous material such as glass cloth, aramid nonwoven fabric or liquid crystal polymer into a fibrous material such as varnish after dissolving an organic solvent, It can be a prepreg. Further, it may be coated on a sheet material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film, as the case may be.

When the epoxy resin composition of the present invention is cured by heating, it can be made into an epoxy resin cured product. The cured product is superior in terms of curability, flame retardancy, low hygroscopicity, and low elasticity. This cured product can be obtained by molding an epoxy resin composition by a method such as molding, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 占 폚.

Example

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

(Synthesis of polyhydric hydroxy resin)

≪ Example 1 >

Phenol novolac (BRG-555, manufactured by Showa Kobo Co., Ltd., hydroxyl group equivalent: 105 g / eq., Softening point: 67 캜, melt viscosity at 150 캜: 0.08 Pa ·) as a polyhydroxy compound component was added to a 1 L four- , Toluene (5.3 g) and 0.078 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst were charged and the temperature was raised to 100 占 폚. Next, 156 g (1.5 mol) of styrene was added dropwise over 3 hours while stirring at 100 캜 and reacted. After further reaction at 100 ° C for 2 hours, 0.071 g of 30% Na ₂ CO ₃ was added to neutralize. Then, the solution was dissolved in 485 g of MIBK and was washed five times at 80 ° C. Subsequently, MIBK was distilled off under reduced pressure to obtain 250 g of a polyhydric hydroxy resin. The hydroxyl group equivalent was 261 g / eq., The softening point was 82 ° C, and the melt viscosity at 150 ° C was 0.21 Pa · s. This resin is referred to as StPN-A. The area% of the monohydric hydroxy compound (2) in the gel permeation chromatography (GPC; RI) measurement was 1.2%. A GPC chart of StPN-A is shown in Fig.

≪ Synthesis Example 1 &

105 g of phenol novolac (BRG-555, manufactured by Showa Kobunshi Co., Ltd.) as a polyhydroxy compound component, 5.3 g of toluene and 0.131 g (500 ppm) of p-toluenesulfonic acid as an acid catalyst were added to a 1 L four- Lt; / RTI > Then, 156 g (1.5 mol) of styrene was added dropwise over 3 hours while stirring at 150 캜, and the reaction was carried out. After reacting at 150 ° C for 2 hours, 0.118 g of 30% Na ₂ CO ₃ was added to neutralize. Then, the solution was dissolved in 485 g of MIBK and was washed five times at 80 ° C. Subsequently, MIBK was distilled off under reduced pressure to obtain 247 g of a polyhydric hydroxy resin. The softening point thereof was 80 ° C, the melt viscosity at 150 ° C was 0.19 Pa · s, and the hydroxyl group equivalent was 261 g / eq. This resin is referred to as StPN-B. In the gel permeation chromatography (GPC; RI) measurement, the area% of the monohydric hydroxy compound (2) was 5.2%. The area% of the styrene dimer was 0.8%. A GPC chart of StPN-B is shown in Fig. In Figs. 1 to 2, A represents the peak of the monohydric hydroxy compound (2), and B represents the peak of the styrene dimer.

(Synthesis of epoxy resin)

≪ Example 2 >

150 g of StPN-A obtained in Example 1, 319 g of epichlorohydrin, and 48 g of diethylene glycol dimethyl ether were placed in a four-necked separable flask and dissolved by stirring. After uniformly dissolving, 47.9 g of a 48% sodium hydroxide aqueous solution was added dropwise over a period of 4 hours while maintaining the temperature at 65 DEG C under a reduced pressure of 130 mmHg. Then, water and epichlorohydrin, which had been refluxed and distilled in this dropwise addition, ; and the epichlorohydrin was returned to the reaction vessel, and water was removed from the system and reacted. After completion of the reaction, the salt produced by the filtration was removed, and after washing with water, epichlorohydrin was distilled off to obtain 172 g of an epoxy resin (StPNE-A). The obtained resin had an epoxy equivalent of 325 g / eq., A softening point of 60 DEG C, and a melt viscosity of 0.19 Pa • at 150 DEG C. The area% of the unit price epoxy compound (5) in the gel permeation chromatography (GPC; RI) measurement was 1.1%. A GPC chart of StPNE-A is shown in Fig.

≪ Synthesis Example 2 &

150 g of StPN-B obtained in Synthesis Example 1, 319 g of epichlorohydrin, and 48 g of diethylene glycol dimethyl ether were placed in a four-necked separable flask and dissolved by stirring. After uniformly dissolving, 47.9 g of a 48% sodium hydroxide aqueous solution was added dropwise over a period of 4 hours while maintaining the temperature at 65 ° C under a reduced pressure of 130 mmHg. The water and epichlorohydrin, which had been refluxed and discharged in the dropwise addition, The drain was returned to the reaction vessel, and the water was removed from the system and reacted. After completion of the reaction, the salt formed by filtration was removed, and after washing with water, the epichlorohydrin was distilled off to obtain 170 g of an epoxy resin (StPNE-B). The obtained resin had an epoxy equivalent of 330 g / eq., A softening point of 57 캜, and a melt viscosity at 150 캜 of 0.18 Pa · s. The area% of the unit price epoxy compound (5) in the gel permeation chromatography (GPC; RI) measurement was 5.0%. The area% of the styrene dimer was 0.6%. A GPC chart of StPNE-B is shown in Fig. 3 to 4, A represents the peak of the unit charge epoxy compound (5), and B represents the peak of the styrene dimer.

≪ Example 3 and Comparative Examples 1 and 2 >

(OCNE; epoxy equivalent: 200, softening point: 65 占 폚) was used as an epoxy resin component, and STPN-A obtained in Example 1 and STPN-B obtained in Synthesis Example 1 were used as a curing agent, Volatile (PN; PSM-4261, manufactured by Kunigakagaku Corporation; OH equivalent: 103, softening point: 82 占 폚) was used. Silica (average particle size of 18 占 퐉) as a filler, triphenylphosphine as a curing accelerator and other additives were kneaded in the form shown in Table 1 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 DEG C and post cured at 175 DEG C for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. Details of the measurement of physical properties are shown below, and the results are shown in Table 2.

1) Molecular weight distribution of polyhydric hydroxy resin and epoxy resin

Three TSKgel SuperHZ2000 (Toso products) and one TSKgel SuperHZ4000 (Toso products) were used as columns, a detector was set as RI, and tetrahydrofuran (THF) was used as a solvent. Flow rate of 0.6 ml / min, and a column temperature of 40 캜.

2) Softening point

And measured by a circular method according to JIS-K-2207 using an automatic softening point device (ASP-M4SP, manufactured by Meehosha Co., Ltd.).

3) Melt viscosity

And measured at 150 캜 using a rotational viscometer of CAP 2000 H type manufactured by BROOKFIELD.

4) Measurement of hydroxyl equivalent

The acetalization with 1.5 mol / L acetyl chloride using 1,4-dioxane as a solvent was carried out using a potentiometric titration apparatus, and the excess acetyl chloride was digested with water and titrated with 0.5 mol / L-potassium hydroxide.

5) Measurement of epoxy equivalence

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

6) Gel time

The epoxy resin composition was added to a plate of a gelation tester (manufactured by Nisshin Kakaku Co., Ltd.) heated to 175 ° C and stirred at a rate of two revolutions per second using a fluorine resin bar to obtain a cured epoxy resin composition The gelation time required until the gel was observed.

7) Coefficient of linear expansion (CTE), glass transition point (Tg)

Tg was calculated with a Seiko Instruments TMA120C thermomechanical measuring apparatus under the condition of a temperature raising rate of 10 DEG C / min. The alpha 1 (CTE below Tg) is an average value in the range of 30 to 50 DEG C and alpha 2 (CTE above Tg) Plus 20 占 폚 to 40 占 폚.

8) Bending strength and bending elasticity

According to JISK 6911, it was measured at room temperature by the three-point bending test.

9) Adhesive strength

A molded article of 25 mm x 12.5 mm x 0.5 mm was molded between two copper plates at 175 DEG C by a compression molding machine and evaluated by determining the tensile shear strength after post curing at 180 DEG C for 12 hours.

10) Absorption rate (water absorption rate)

25 deg. C and 50% relative humidity was set to the standard state, and the weight change rate after moisture absorption at 85 deg. C and 85% relative humidity for 100 hours was determined.

11) Flammability

A 1/16 inch thick test piece was molded and evaluated according to UL94V-0 standard, and expressed as the total burning time in five test pieces.

≪ Examples 4 and 5 and Comparative Examples 3 and 5 >

Cresol novolak type epoxy resin (OCNE; epoxy equivalent: 200, softening point: 65 占 폚) was used in place of StPNE-A obtained in Example 2 and StPNE-B obtained in Synthesis Example 2 as epoxy resin components, (OH: equivalent weight: 175, softening point: 67 ° C) or phenol novolac (PN: PSM-4261 (manufactured by Mitsui Eikagaku) OH equivalent: 103, softening point: 82 ° C) Respectively. Also, spherical silica (average particle size of 18 mu m) was used as a filler and triphenylphosphine was used as a curing accelerator. An epoxy resin composition was obtained from the compositions shown in Table 3. The numerical values in the table indicate the parts by weight in the blend.

This epoxy resin composition was molded at 175 캜, and further subjected to post cure at 175 캜 for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 4.

The epoxy resin and the polyhydric hydroxy resin of the present invention are applied to an epoxy resin composition to give a cured product excellent in curability and excellent in flame retardance, moisture resistance, and low elasticity, and used for encapsulating electric and electronic parts, Can be preferably used. In particular, it is excellent in curability and flame retardancy, and while ensuring excellent moldability, the use of a flame retardant having an environmental load is dispensed with or reduced.

Claims (9)

1. An epoxy resin represented by the following general formula (4), wherein the unit epoxy resin represented by the following general formula (5) is not more than 3% by area% when it is detected by gel permeation chromatography Suzy.

R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; R ₂ represents a substituent represented by the formula (a); and n represents a number of 1 to 20, wherein G represents a glycidyl group, R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, And p represents a number of 0.1 to 2.5. R ₃ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

Here, G represents a glycidyl group, p represents a number of 0 to 3, and R ₁ and R ₃ represent hydrogen or a hydrocarbon group of 1 to 6 carbon atoms. A polyhydroxy resin having an epoxy equivalent of 3% or less as measured by gel permeation chromatography (GPC) (RI) and represented by the following general formula (1) and a monohydric hydroxy compound represented by the following general formula (2) Chlorohydrin is reacted with the hydroxyl group of the polyhydric hydroxy resin to obtain a glycidyl ether group.

Here, R ₁ represents hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, R ₂ represents a substituent represented by the formula (a), and n represents a number of 1 to 20. And p represents a number of 0.1 to 2.5. R ₃ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

Here, p represents a number of 0 to 3, and R ₁ and R ₃ represent hydrogen or a hydrocarbon group of 1 to 6 carbon atoms. An epoxy resin composition comprising an epoxy resin and a curing agent, the epoxy resin composition comprising the epoxy resin according to claim 1 as an essential component. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 3. delete delete delete delete delete

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