TWI522397B - A polyhydroxy resin, an epoxy resin, a manufacturing method thereof, an epoxy resin composition and a hardened product - Google Patents

Description

Polyvalent hydroxy resin, epoxy resin, manufacturing method of the same, epoxy resin composition and cured product thereof

The present invention relates to an epoxy resin which imparts a cured product having excellent hardenability, excellent flame retardancy, moisture resistance and low elasticity, and is suitable as a multi-component hydroxy resin which is an intermediate thereof, and a manufacturing method thereof. The epoxy resin composition and the cured product thereof are suitable for insulating materials such as semiconductor encapsulants, printed wiring boards, and the like in the field of electrical and electronic materials.

Industrially, epoxy resins have been used in a wide range of applications, but in recent years their performance has been gradually improved. For example, a semiconductor encapsulating material in a representative field of a resin composition containing an epoxy resin as a main component, but with an increase in the degree of integration of the semiconductor element, the casing tends to be large-area and thin, and the mounting method is also Development towards the surface has been developed, so it is expected to develop materials with excellent solder heat resistance. Therefore, in addition to low moisture absorption, the encapsulating material is strongly required to improve the bonding property and adhesion to the interface of the different materials such as the lead frame and the sheet. Similarly, in view of the fact that the circuit board material can improve low heat absorption, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance, it is possible to develop a material having excellent low dielectric properties from the viewpoint of reducing dielectric loss. . Various novel constructions of epoxy resins and hardeners are reviewed in response to such requirements. In addition, recently, in order to reduce the environmental load, it is possible to promote the elimination of halogen-based flame retardants, and to obtain more excellent flame retardant epoxy resins and hardeners.

Review various epoxy resins and epoxy resin hardeners based on the above background. The epoxy resin hardener is, for example, a known naphthalene resin. Patent Document 1 discloses that a naphthol aralkyl ester resin can be used for a semiconductor encapsulant to obtain excellent flame retardancy, low hygroscopicity, low thermal expansion property, and the like. Further, Patent Document 2 describes that the proposed hardener having a biphenyl structure can effectively improve flame retardancy. However, the naphthol aralkyl ester resin and the biphenyl aralkyl ester resin have the disadvantages of poor hardenability, and the effect of improving the flame retardancy is insufficient.

On the other hand, there is no such thing as an epoxy resin that meets these requirements. For example, a known bisphenol type epoxy resin is liquid at normal temperature, has excellent workability, and is easily used in combination with a curing agent, an additive, etc., but has problems of heat resistance and moisture resistance. Further, an o-cresol novolac type epoxy resin is known as an improved heat resistance, but the flame retardancy is insufficient.

A countermeasure against the use of a halogen-based flame retardant to improve the flame retardancy has revealed that a phosphate-based flame retardant is added. However, the method of using a phosphate-based flame retardant is insufficient in moisture resistance. Further, in a high-temperature, high-humidity environment, the phosphate ester is hydrolyzed, and there is a problem that the reliability of the insulating material is lowered.

A material which can improve the flame retardancy without containing a phosphorus atom and a halogen atom. For example, as disclosed in Patent Documents 2 and 3, an aralkyl type epoxy resin having a biphenyl structure is used as an example of a semiconductor encapsulant. Patent Document 4 discloses an example of using an aralkyl type epoxy resin having a naphthalene structure. However, the performance of these epoxy resins for flame retardancy, moisture resistance or heat resistance is still insufficient.

Further, attention is directed to the improvement of heat resistance, moisture resistance, and crack resistance. For example, the benzylated polyphenol and the epoxy resin disclosed in Patent Document 5 are not focused on the flame retardant. Further, these are resins obtained by using a phenol novolak as a starting material, and then a benzyl chloride is subjected to an addition reaction. Since the hydrochloric acid generated during the reaction is used as a catalyst, the reaction is carried out under strong acidic conditions. The methene novolac methacrylate crosslink bond is partially cracked, and there is a problem of by-product phenol. That is, since the monofunctional phenol body containing a by-product has a problem of lowering the curability and heat resistance.

Further, in the method for producing a styrene-modified novolac, as disclosed in Patent Document 6, there is a method in which a phenol novolak is reacted with styrene under an acid catalyst, but in the present method using a highly acidic sulfuric acid catalyst at a high temperature, The cross-linking of the metene bond of the phenol novolak is partially cracked and there is a problem of by-produced phenol.

Further, an epoxy resin composition which improves moisture resistance and low stress is disclosed. Patent Literatures 7 and 8 disclose an epoxy resin composition using a styrenated phenol novolak resin and an epoxy resin thereof, but these are not Focus on flame retardancy. Moreover, since these are the raw materials which use styrene-formed phenol as a starting material, and the phenol aldehyde varnish is formed after this, the high-boiling styrene phenol remains in the resin, and the problem of the hardening property and heat resistance fall.

Prior technical literature

[Patent Document 1] JP-A-2005-344081

[Patent Document 2] Japanese Patent Publication No. 11-140166

[Patent Document 3] JP-A-2000-129092

[Patent Document 4] JP-A-2004-59792

[Patent Document 5] Japanese Patent Publication No. 8-120039

[Patent Document 6] JP-A-48-52895

[Patent Document 7] Japanese Patent Laid-Open No. Hei 5-132544

[Patent Document 8] Japanese Patent Publication No. 5-140265

Summary of invention

An object of the present invention is to provide an epoxy resin having excellent hardenability, excellent flame retardancy, moisture resistance, low elasticity, and the like in lamination, molding, injection molding, bonding, and the like, and to provide an epoxy resin. An epoxy resin composition suitable for packaging of electric and electronic components, circuit board materials, and the like, and a cured product thereof, which are excellent in hardenability and excellent in flame retardancy, moisture resistance, and low elasticity.

In other words, in the polyhydric hydroxy resin represented by the following general formula (1), the monovalent (monobasic) hydroxy compound represented by the following general formula (2) is examined by gel permeation chromatography (GPC; RI). The polyvalent hydroxy resin having an area % of 3% or less.

【化1】

(R ₁ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ is a substituent represented by the following formula (a), n is a number from 0 to 20. p is a number from 0.1 to 2.5. Further, R ₃ is Hydrogen or a hydrocarbon group having 1 to 6 carbon atoms).

[Chemical 2]

(wherein p is a number from 0 to 3, and R ₁ and R ₃ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms).

Further, the present invention is characterized in that it is characterized in that it has a reaction temperature of 40 to 120 ° C in the presence of an acid catalyst of 10 to 400 wt ppm or less with respect to the hydroxyl group 1 mol of the polyvalent hydroxy compound represented by the following general formula (3). A method for producing a polyvalent hydroxy resin in which a styrene is reacted in an amount of 0.1 to 1.0 mol, and a benzene ring of a polyvalent hydroxy compound is substituted with a substituent represented by the above formula (a).

[化3]

Further, the present invention is characterized in that, in the epoxy resin represented by the following general formula (4), the monovalent (mono) epoxy resin represented by the following general formula (5) is subjected to gel permeation chromatography (GPC; RI). The epoxy resin having an area % of 3% or less at the time of inspection.

【化4】

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

【化5】

(wherein G is a glycidyl group, R ₁ and R ₃ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and p is a number of 0 to 3).

Further, the present invention relates to a method for producing an epoxy resin in which the above polyhydric hydroxy resin is reacted with epichlorohydrin.

Further, the present invention relates to an epoxy resin composition obtained by adding one or both of the above-mentioned polyvalent hydroxy resin and the above epoxy resin to an epoxy resin composition formed of an epoxy resin and a curing agent. Further, the present invention relates to an epoxy resin cured product obtained by curing the above epoxy resin composition.

Form of implementing the invention

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

The method of adding styrene to a polyvalent hydroxy compound is generally carried out at a high temperature of 120 to 170 ° C in the presence of an acid catalyst such as hydrochloric acid. However, when the reaction is carried out at a high temperature under an acid catalyst, the methylene bond of the linking group portion of the polyvalent hydroxy compound is cracked, and there is a problem of by-product phenol. In order to suppress such side reactions, the by-product phenolic body can be reduced by lowering the reaction temperature to 40 to 120 ° C and reducing the amount of the catalyst to 10 to 400 ppm. In other words, when the obtained polyvalent hydroxy resin is used as a curing agent for an epoxy resin, physical properties of excellent curability and heat resistance can be found.

The monovalent hydroxy compound (also referred to as monobasic hydroxy compound (2)) represented by the above general formula (2) produced by the side reaction is preferably contained in the polyhydric hydroxy resin component by gel permeation chromatography (GPC; RI). The area % at the time of inspection is 3% or less. When the amount is more than this value, when the polyvalent hydroxy resin is used as the epoxy resin curing agent, the by-product monovalent hydroxy compound contained tends to lower the curability. Further, the monovalent hydroxy compound in the cured epoxy resin also lowers the crosslinking density, and tends to deteriorate heat resistance.

A component other than the monovalent hydroxy compound in the by-product contained in the polyhydric hydroxy resin is, for example, a styrene oligomer. It is a by-product formed by the polymerization of styrene itself, especially a styrene dimer containing a low molecular weight component. The styrene dimer component is also a hydroxy compound which tends to lower the cured product and heat resistance.

Further, in the cured epoxy resin, the hydroxypropyl group formed by the reaction of the epoxy group with the hydroxyl group is flammable, but the addition of styrene to the polyvalent hydroxy compound increases the hydroxyl equivalent and reduces the flammability from the epoxy group. The aliphatic carbon ratio of the component can be found to be highly flame retardant. Further, by adding aromatic styrene, the aromaticity of the polyhydric hydroxy resin can be further improved, so that moisture resistance can be effectively improved in addition to flame retardancy.

Therefore, it is possible to use such an epoxy resin composition which is highly flame retardant, in particular, an epoxy resin composition for semiconductor encapsulation. In other words, the composition can be found to have excellent curability, high flame retardancy, moisture resistance, and low elasticity, and the use of the material can provide a highly reliable electrical and electronic component package, a circuit board material, and the like.

The StPN of the present invention is obtained by addition of a polyvalent hydroxy compound (3) represented by the general formula (3) to a styrene compound. In this case, the ratio of the polyvalent hydroxy compound (3) to the styrene is considered to be a balance between the flame retardancy and the hardenability of the obtained cured product, and the ratio of the styrene to the polyvalent hydroxy compound 1 mole is preferably 0.1 to 2.5 moles, preferably 0.1 to 1.0 moles, more preferably 0.3 to 0.8 moles. When the amount is less than this range, the polyvalent hydroxy compound of the raw material cannot be improved and maintained in the original state. When the content is more than this range, the density of the functional group is too low and the curability is lowered.

In the reaction, styrene is added to the aromatic ring having an OH group in the polyvalent hydroxy compound (3), and is substituted with a styryl group represented by the above formula (a). Further, the addition position of the styrene is a positive and/or a para position of the vacancy of the polyvalent hydroxy compound, but is mainly a para position.

Further, the StPN of the present invention preferably has a melt viscosity at 150 ° C of 0.01 to 10.0 Pa‧s. In terms of workability, the melt viscosity is preferably the lower of the above range.

Further, the softening point may be from 40 to 150 ° C, preferably from 50 to 100 ° C. The softening point at this time means a softening point measured based on the ring method of JIS-K-2207. Below this, when the epoxy resin is added, the heat resistance of the cured product is lowered, and when it is higher than this, the fluidity at the time of molding is lowered.

R ₂ is a styrene group represented by the above formula (a). p is an integer from 0.1 to 2.5, but it refers to the average number (number average) of the styryl groups substituted on one phenol ring. The p order is preferably from 0.1 to 2, from 0.1 to 1.0 mol, from 0.3 to 1, from 0.3 to 0.8 mol. Further, the phenol ring at both ends may be substituted with up to 4 styryl groups, and the intermediate phenol ring may be substituted with up to 3 styryl groups, so that when n is 1, it may be substituted with up to 8 styryl groups.

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

In the formula (a), R ₃ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. This R ₃ is determined by the styrene used for the reaction raw materials used.

In the general formula (1), n is an integer of 1 to 20, preferably an average of 1.5 to 5.0.

Next, a method of manufacturing the StPN of the present invention will be explained. The polyvalent hydroxy compound (3) used in the method for producing StPN of the present invention is a phenol novolak.

The phenols used in the production of the polyvalent hydroxy compound (3) are phenol or a hydrocarbyl substituted phenol having a carbon number of 1 to 6, and a hydrocarbyl-substituted phenol such as a cresol, an ethylphenol, an isopropylphenol or a t-butylphenol. Classes, allyl phenols, phenylphenols, and the like. Preferably, the phenol or the alkyl group having 1 to 3 carbon atoms is substituted with a phenol, more preferably phenol.

The phenol may contain a small amount of other phenol components. For example, when the phenol used is phenol, other phenol components such as o-cresol, m-cresol, p-cresol, ethylphenol, isopropylphenol, tert-butylphenol, allylic Phenolic phenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcinol, catechol, 1-naphthol, 2-naphthol, 1, 5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, and the like. These phenols or naphthols may contain two or more types.

The styrene used for the reaction with the polyvalent hydroxy compound is styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms. The styrene may contain small amounts of other reactive components. When the other reaction component contains an unsaturated bond component such as α-methylstyrene, divinylbenzene, anthracene, coumarone, benzothiophene, anthracene or vinylnaphthalene, the obtained polyhydric hydroxy resin may contain A compound substituted on the aromatic ring by the groups formed. The phenol resin obtained by the method for producing a polyvalent hydroxy resin of the present invention contains a polyvalent hydroxy resin having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention contains an epoxy resin having such a substituent.

The reaction can be carried out in the presence of an acid catalyst, and the amount of the catalyst used is from 10 to 400 ppm, preferably from 100 to 350 ppm. When the value is more than this value, the methene crosslink bond of the phenol novolak is easily cracked, and the monovalent phenol component by-produced by the cracking reaction lowers the hardenability and heat resistance. Further, less than this value lowers the reactivity, and a large amount of unreacted styrene monomer remains. Further, the amount of the catalyst at this time means the amount of the catalyst relative to the total weight of the polyvalent hydroxy compound for reaction and the styrene.

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

Further, the reaction is carried out at a reaction temperature of 40 to 120 °C. Below this value, the reactivity is lowered and the reaction time is long. Further, when the value is higher than this value, the crosslink of the methylene crosslink of the phenol novolak is easily broken, and the monovalent phenol component by-produced by the cracking reaction lowers the hardenability and heat resistance.

Further, the reaction is generally carried out for 1 to 20 hours. Further, an alkyl alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve may be used for the reaction, and acetone, methyl ethyl ketone or methyl isobutyl group may be used. a solvent such as a ketone or the like, an ether such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran or dioxane, or an aromatic compound such as benzene, toluene, chlorobenzene or dichlorobenzene. .

The specific method for carrying out the reaction is generally a method in which a reaction is carried out directly after charging all the raw materials, or a polyvalent hydroxy compound and a catalyst are charged, and a styrene is dropped at a constant temperature to carry out a reaction. The dropping time at this time is preferably 5 hours or less, and is usually 1 to 10 hours. When a solvent is used after the reaction, if necessary, the catalyst component is removed and the solvent is distilled off to obtain the resin of the present invention. When the solvent is not used, it can be directly discharged during heat to obtain the object.

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

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

In the general formula (4), the symbol is common to the general formula (1). G is a glycidyl group, but is formed by reacting with a hydroxyl group of the general formula (1). R ₁ is a styryl group.

The StPNE of the present invention is suitably produced by reacting StPN represented by the above general formula (1) with epichlorohydrin, and is not limited to the reaction. However, the above-mentioned monohydric hydroxy compound contained in StPN does not exceed 3%. Therefore, the monovalent epoxy resin (also referred to as a monovalent epoxy resin (5)) represented by the above general formula (5) is 3% or less.

In addition to reacting StPN with epichlorohydrin, a method in which StPN is reacted with an allyl halide to form an allyl ether and reacted with a peroxide can be used. The reaction of the above StPN with epichlorohydrin is generally carried out by an epoxidation reaction.

For example, after dissolving the above StPN in an excess of epichlorohydrin, reacting in an amount of from 20 to 150 ° C, preferably from 30 to 80 ° C, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The method of hours. The alkali metal hydroxide is used in this case in an amount of from 0.8 to 1.5 mol, preferably from 0.9 to 1.2 mol, based on the hydroxyl group of the StPN. Further, epichlorohydrin is used in excess with respect to the hydroxyl group 1 mole in StPN, but is generally 1.5 to 30 moles, preferably 2 to 15 moles, per mole of hydroxyl group 1 in StPN. After the completion of the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off to obtain the desired epoxy. Resin.

The epoxy resin composition of the present invention contains at least an epoxy resin and a hardener, and has the following three types.

1) Adding one or both of the epoxy resins to the composition obtained by the aforementioned StPNE.

2) Adding a composition obtained by partially or completely using the aforementioned StPN.

3) Adding a composition obtained by partially or completely using the above-mentioned SPE and StPN, one of epoxy resin and hardener.

In the case of the compositions of the above 2) and 3), StPN is an essential component. The amount of StPN added is generally 2 to 200 parts by weight, preferably 5 to 80 parts by weight, per 100 parts by weight of the epoxy resin. When the value is less than this value, the effect of improving the flame retardancy and the moisture resistance is reduced, and when it exceeds this value, there is a problem that the formability and the strength of the cured product are lowered.

When StPN is used in the total amount of the hardener, the amount of StPN added is generally added in consideration of the equivalence balance between the OH group of StPN and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin to the hardener is generally from 0.2 to 5.0, preferably from 0.5 to 2.0. When the value is larger than this value, the hardenability of the epoxy resin composition, the heat resistance and mechanical strength of the cured product, and the like are lowered.

The hardener may be used in combination with a hardener other than StPN. The amount of other hardener added is generally determined by the amount of StPN added in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight, per 100 parts by weight of the epoxy resin. When the amount of StPN added is less than this value, the effect of improving the hygroscopicity, the adhesion, and the flame retardancy is reduced. When the amount is more than this value, there is a problem that the moldability and the strength of the cured product are lowered. The equivalent ratio of the epoxy resin to the hardener (total) at this time is also in the above range.

As the hardener other than StPN, those commonly used in hardeners of epoxy resins such as dicyandiamide, acid anhydrides, polyvalent phenols, aromatic and aliphatic amines, and the like can be used. Among them, in the field of high electrical insulating properties requiring semiconductor encapsulants and the like, the hardener is preferably a polyvalent phenol. The following are specific examples of the hardener.

An acid anhydride hardener such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl bicycloheptenediphthalic anhydride, dodecyl succinic anhydride, bare anhydride, Trimellitic anhydride and the like.

Polyvalent phenols such as bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol A, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone, resorcinol, naphthalenediol Divalent phenols, or tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthalene A trivalent or higher phenol represented by a phenol novolak or a polyvinyl phenol. For example, phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone, resorcinol, Synthesis of divalent phenols such as naphthalenediol and condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylene dichloride, bischloromethylbiphenyl, and dichloromethylnaphthalene The obtained polyvalent phenolic compound or the like.

Amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylanthracene, m-phenylenediamine An aliphatic amine such as an aromatic amine such as p-xylylenediamine, an ethylenediamine, a hexamethylenediamine, a di-ethyltriamine or a diethylethamine.

In the above composition, the curing agents may be used singly or in combination of two or more kinds.

The epoxy resin used in the above 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, bismuth bisphenol, 2,2'-bisphenol, 3,3',5 , a bivalent phenolic epoxide such as 5'-tetramethyl-4,4'-dihydroxybiphenyl, resorcinol or naphthalenediol, tris-(4-hydroxyphenyl)methane, 1, Covalent condensation of trivalent or higher phenolic epoxides, dicyclopentadiene and phenols, such as 1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, and o-cresol novolac An epoxide of a resin, an epoxide of a phenol aralkyl ester resin synthesized from a phenol or a p-xylene dichloride, a biphenyl aralkyl type phenol synthesized from a phenol or a bischloromethylbiphenyl An epoxide such as a resin epoxide, a naphthol, a p-xylene dichloride or the like, and an epoxide of a naphthol aralkyl ester resin. These epoxy resins may be used singly or in combination of two or more kinds.

In the composition of the above 1) and 3), the StPNE contained is an essential component. In the epoxy resin composition, other kinds of epoxy resins may be added in addition to StPNE. The epoxy resin at this time can be used as a substance in a general epoxy resin having two or more epoxy groups in the molecule. For example, bisphenol A, bisphenol S, bisphenol, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone, resorcinol, etc., divalent phenol, or tris-(4-hydroxyl) a trivalent or higher phenol or a phenol aralkyl ester resin such as phenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, a phenol novolak, or an o-cresol novolak; A glycidyl ether compound derived from a biphenyl aralkyl ester resin, a naphthol aralkyl ester resin, or a halogenated bisphenol such as tetrabromobisphenol A. These epoxy resins may be used singly or in combination of two or more kinds. Further, in the composition of the present invention in which StPNE is an essential component, the amount of StPNE added may be 5 to 100%, preferably 60 to 100%, based on the entire epoxy resin.

The epoxy resin composition of the present invention may be appropriately added with a polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, an anthracene resin, a quinone-coumarin resin, a phenoxy resin. Other modifiers such as oligomers or polymer compounds. The amount added is generally 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

Further, an additive such as an inorganic filler, a pigment, a flame retardant, a shake imparting agent, a coupling agent, or a fluidity enhancer may be added to the epoxy resin composition of the present invention. Inorganic fillers such as spherical or broken molten cerium oxide, cerium oxide powder such as cerium oxide, alumina powder, glass powder or mica, talc, calcium carbonate, alumina, hydrated alumina, etc., used The amount of the semiconductor encapsulant added is preferably 70% by weight or more, more preferably 80% by weight or more.

The pigment is, for example, an organic or inorganic extender pigment, a flaky pigment, or the like. The shake imparting agent is, for example, a lanthanide, a castor oil, an aliphatic guanamine wax, an oxidized polyethylene wax, an organic bentonite or the like.

Further, if necessary, a curing accelerator can be used for the epoxy resin composition of the present invention. For example, amines, imidazoles, organic phosphines, Lewis acids, etc., for example, 1,8-diazabicyclo(5,4,0) undecene-7, tri-ethylidene diamine, benzyl Tertiary amine such as dimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4 - imidazoles such as methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, Tetrasubstituted anthracene-four such as an organic phosphine such as phenylphosphine, tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate or tetrabutylphosphonium-tetrabutylborate A tetraphenylboron salt such as a borate, 2-ethyl-4-methylimidazolium-tetraphenylborate or N-methylmorpholine-tetraphenylborate. The amount added is generally 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

Further, if necessary, a resin composition of the present invention may be a release agent such as carnauba wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxydecane, or a coloring agent such as carbon black or the like. A flame retardant such as cerium oxide, a low stress agent such as eucalyptus oil, or a slip agent such as calcium stearate.

After dissolving the epoxy resin composition of the present invention in an organic solvent to form a lacquer state, the fiber is impregnated with a fibrous material such as a glass hybrid, a polyamide non-woven fabric, or a liquid crystal polymer, and the solvent is removed. Prepreg. Further, the laminate may be applied to a sheet such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film, as the case may be.

The epoxy resin composition of the present invention is heat-cured to obtain an epoxy resin cured product. The cured product has excellent hardenability, flame retardancy, low moisture absorption, low elasticity, and the like. The cured product can be obtained by molding an epoxy resin composition by injection molding, compression molding, transfer molding, or the like. The temperature at this time is generally from 120 to 220 °C.

Example

The invention will now be described more specifically by way of examples.

(Synthesis of polyhydroxy resin) Example 1

A phenol novolak (manufactured by Showa Polymer, BRG-555, hydroxyl equivalent 105 g/eq., softening point 67 ° C, melt viscosity at 150 ° C, 0.08 Pa‧s) of a polyvalent hydroxy compound component, 105 g, toluene 5.3 g, acid touch 0.078 g (300 ppm) of p-toluenesulfonic acid was added to a 1 L four-necked flask and the temperature was raised to 100 °C. Next, while stirring at 100 ° C, 156 g (1.5 mol) of styrene was dropped into the mixture for 3 hours to carry out a reaction. Further, after reacting at 100 ° C for 2 hours, 0.071 g of 30% Na ₂ CO _{3 was} added for neutralization. Then, it was dissolved in 485 g of MIBK, and further washed with water 5 times at 80 °C. Thereafter, MIBK was distilled off under reduced pressure to obtain 250 g of a polyhydric hydroxy resin. The hydroxyl equivalent was 261 g/eq., the softening point was 82 ° C, and the melt viscosity at 150 ° C was 0.21 Pa·s. The resin is referred to as StPN-A. As a result of gel permeation chromatography (GPC; RI), the area % of the monovalent hydroxy compound (2) was 1.2%. The GPC chart of StPN-A is shown in Figure 1.

Synthesis Example 1

105 g of a phenol novolak (BRG-555) of a polyvalent hydroxy compound component, 5.3 g of toluene, and 0.131 g (500 ppm) of p-toluenesulfonic acid of an acid catalyst were placed in a 1 L four-necked flask, and the temperature was raised to 150 ° C. Next, while stirring at 150 ° C, 156 g (1.5 mol) of styrene was dropped into the mixture for 3 hours to carry out a reaction. After further reacting at 150 ° C for 2 hours, 0.118 g of 30% Na ₂ CO _{3 was} added for neutralization. Then, it was dissolved in MIBK 485g, and washed with water 5 times at 80 °C. Thereafter, MIBK was distilled off under reduced pressure to obtain 247 g of a polyhydric hydroxy resin. The softening point was 80 ° C, the melt viscosity at 150 ° C was 0.19 Pa ‧ and the hydroxyl equivalent was 261 g / eq. The resin is referred to as StPN-B. As a result of gel permeation chromatography (GPC; RI), the area % of the monovalent hydroxy compound (2) was 5.2%. Further, the area % of the styrene dimer was 0.8%. The GPC chart of StPN-B is shown in Figure 2. In Figs. 1 to 2, A is a peak of a monovalent hydroxy compound (2), and B is a peak of a styrene dimer.

(synthetic 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-neckable flask and stirred to dissolve. After uniformly dissolving, the solution was kept at 65 ° C under a reduced pressure of 130 mmHg, and 47.9 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. The liquid was distilled off and the epichlorohydrin was separated by a separation tank while the solution was dropped. The oxychloropropane is returned to the vessel, and the water is removed to the outside of the system for reaction. After completion of the reaction, the salt formed by the filtration was removed, and the water-washed epichlorohydrin was distilled off to obtain 172 g (StPNE-A) epoxy resin. The obtained resin had an epoxy equivalent of 325 g/eq., a softening point of 60 ° C, and a melt viscosity at 150 ° C of 0.19 Pa·s. The area % of the monovalent epoxy compound (5) was 1.1% as measured by gel permeation chromatography (GPC; RI). The GPC chart of StPNE-A is shown in Figure 3.

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-neckable flask and stirred to dissolve. After uniformly dissolving, the solution was kept at 65 ° C under reduced pressure of 130 mmHg, and 47.9 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. The liquid was separated from the epichlorohydrin by separating the refluxed water and epichlorohydrin in the separation tank. The chloropropane is returned to the reaction vessel, and the water is removed to the outside of the system for reaction. After the completion of the reaction, the salt formed by the filtration was removed, and the water-washed 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 ° C, and a melt viscosity at 150 ° C of 0.18 Pa ‧ . The area % of the monovalent epoxy compound (5) was 5.0% as measured by gel permeation chromatography (GPC; RI). Further, the area % of the styrene dimer was 0.6%. The GPC chart of StPNE-B is shown in Figure 4. In Figs. 3 to 4, A is a peak of the monovalent epoxy compound (5), and B is a peak of a styrene dimer.

Example 3 and Comparative Examples 1, 2

The epoxy resin component used was an o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point: 65 ° C), and the hardener was used in addition to STPN-A obtained in Example 1 and STPN-B obtained in Synthesis Example 1. Phenolic novolac (PN; PSM-4261 (manufactured by QunGong Chemical Co., Ltd.; OH equivalent 103, softening point 82 ° C). An epoxy resin composition was obtained by kneading a cerium oxide (average particle diameter: 18 μm) to which a filler was added as shown in Table 1, triphenylphosphine of a hardening accelerator, and other additives. The epoxy resin composition was molded at 175 ° C, and further cured at 175 ° C for 12 hours to obtain a cured test piece, and various physical properties were measured. The details of the physical property measurement are as follows, and the results are shown in Table 2.

1) Molecular weight distribution of polyhydroxy resin and epoxy resin

A GPC measuring device (G/C, Model 515A, Japan) was used, and one tube was used for TSKgel Super HZ2000 (manufactured by Tosoh Corporation), one TSKgel SuperHZ4000 (manufactured by Tosoh Corporation), the tester was RI, and the solvent was tetrahydrofuran. The measurement was carried out under the conditions of a column temperature of 40 ° C at 0.6 ml/min.

2) Softening point

The automatic softening point apparatus (manufactured by Mingfeng Co., Ltd., ASP-M4SP) was used in accordance with JIS-K-2207 to measure by the ring method.

3) Melt viscosity

The CAP2000H rotary viscometer, manufactured by BROOKFIELD, was measured at 150 °C.

4) Determination of hydroxyl equivalent

Using a potentiometric titration apparatus, the solvent was 1,4-dioxane, and after acetonitrileization with 1.5 mol/L of ethyl hydrazine chloride, the excess acetonitrile was decomposed by water, and titration was carried out using 0.5 mol/L of potassium hydroxide.

5) Determination of epoxy equivalent

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

6) Gel time

The epoxy resin composition was placed on a hot plate of a gelation tester (manufactured by Nisshin Scientific Co., Ltd.) heated to 175 ° C, and stirred at a speed of one second and two revolutions using a fluororesin rod to investigate the epoxy resin composition. The gelation time required for the hardening of the object.

7) Linear expansion coefficient (CTE, glass transition point (Tg))

Using Tektronix TMA120C thermomechanical measuring device, Tg was obtained at a temperature rising rate of 10 ° C / min, and α1 (CTE below Tg) was obtained from the average value of 30 to 50 ° C, and Tg + 20 ° C The average value to 40 ° C was taken to obtain α 2 (CTE above Tg).

8) Flexural strength and elasticity

According to JIS K6911, it was measured at room temperature by a 3-point bending test method.

9) Joint strength

A molded product of 25 mm × 12.5 mm × 0.5 mm between two steel sheets was molded at 175 ° C using a compression molding machine, and further heat-cured at 180 ° C for 12 hours to obtain tensile shear strength.

10) Water absorption rate

The weight change rate after moisture absorption for 100 hours under the conditions of 85 ° C and a relative humidity of 85% was determined under the conditions of 25 ° C and a relative humidity of 50%.

11) Flame retardancy

After the test piece having a thickness of 1/16 inch was molded, it was evaluated according to the UL94V-0 specification, and then expressed by the total burning time of the five test pieces.

Examples 4 and 5 and Comparative Examples 3 to 5

The epoxy resin component was an o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C) in addition to StPNE-A obtained in Example 2 and StPNE-B obtained in Synthesis Example 2. The hardener component is a phenol aryl aralkyl ester resin (PA; MEH-7800SS (manufactured by Megumi Chemical Co., Ltd., OH equivalent 175, softening point: 67 ° C) or phenol novolac (PN; PSM-4261 (manufactured by Kyoei Chemical Co., Ltd.), OH equivalent 103, softening point 82 ° C). Further, as the filler, spherical cerium oxide (average particle diameter: 18 μm) was used, and for the curing accelerator, triphenylphosphine was used. The epoxy resin composition was added as shown in Table 3. The values in the table are the added parts by weight.

The epoxy resin composition was molded at 175 ° C, and further cured at 175 ° C for 12 hours to obtain a cured test piece, and various physical properties were measured. The results are shown in Table 4.

Industrial use possibility

When the epoxy resin and the polyvalent hydroxy resin of the present invention are used in an epoxy resin composition, they can provide a cured product which is excellent in hardenability and has excellent flame retardancy, moisture resistance and low elasticity, and is suitable for packaging of electric and electronic components. Use of circuit board materials, etc. In particular, it has excellent hardenability and flame retardancy, and ensures excellent moldability, and does not require or reduce the use of a flame retardant having an environmental load.

Figure 1 is a GPC chart of the polyhydric hydroxy resin obtained in the examples.

Fig. 2 is a GPC chart of the polyhydric hydroxy resin obtained in the synthesis example.

Figure 3 is a GPC chart of the epoxy resin obtained in the examples.

Fig. 4 is a GPC chart of the epoxy resin obtained in the synthesis example.

Claims (6)

A polyhydric hydroxy resin which is a polyhydric hydroxy resin represented by the following general formula (1), characterized in that styrene is 0.1 to 1.0 mol relative to each other in the presence of an acid catalyst of 10 to 400 wt ppm The hydroxyl group 1 of the polyvalent hydroxy compound represented by the following general formula (3) is obtained by reacting at a reaction temperature of 40 to 120 ° C, and the monovalent (mono) hydroxy compound represented by the following general formula (2) is subjected to gel permeation chromatography. The area % of the method (GPC; RI) test is 3% or less. (wherein R ₁ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ is a substituent represented by the formula (a), n is a number from 0 to 20, p is a number from 0.1 to 2.5, and R ₃ is hydrogen Or a hydrocarbon group having 1 to 6 carbon atoms); (wherein p is a number from 0 to 3, and R ₁ and R ₃ are hydrogen or a hydrocarbon group having from 1 to 6 carbon atoms); (wherein R ₁ and R ₃ are a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n is a number from 1 to 20). An epoxy resin composition characterized in that, in an epoxy resin composition formed by 100 parts by weight of an epoxy resin and 2 to 200 parts by weight of a curing agent, part or all of the hardener is as claimed in the patent application. The polyhydroxy resin of the item is obtained as an essential component. An epoxy resin cured product obtained by hardening an epoxy resin composition as in the second aspect of the patent application. An epoxy resin which is an epoxy resin represented by the following general formula (4), characterized in that styrene is 0.1 to 1.0 mol relative to the lower side in the presence of an acid catalyst of 10 to 400 wt ppm The hydroxyl group 1 of the polyvalent hydroxy compound represented by the general formula (3) is reacted at a reaction temperature of 40 to 120 ° C, and the obtained polyhydric hydroxy resin is further reacted with epichlorohydrin, and the following general formula (5) is obtained. The unit area (unitary) epoxy resin represented by the gel permeation chromatography is 3% or less. (wherein G is a glycidyl group, R ₁ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ is a substituent represented by the formula (a), n is a number from 0 to 20, and further, p is 0.1 to 2.5, R ₃ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) (wherein G is a glycidyl group, p is a number from 0 to 3, and R ₁ and R ₃ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms). An epoxy resin composition which is an epoxy resin composition formed by 100 parts by weight of an epoxy resin and 2 to 200 parts by weight of a curing agent, and an epoxy resin added as an essential component as in claim 4 . An epoxy resin cured product obtained by hardening an epoxy resin composition as in item 5 of the patent application.