KR20130108377A - Epoxy resin composition and cured substance - Google Patents

Abstract

The present invention provides an epoxy resin composition which exhibits excellent fluidity and curability, exhibits excellent flame retardancy in a non-halogen system, and is useful for semiconductor encapsulating materials, molding materials, laminated materials, powder coatings, and adhesive materials.
The epoxy resin component contains the epoxy resin represented by following General formula (1) and the bifunctional crystalline epoxy resin whose melt viscosity in 150 degreeC is 0.001-0.05 Pa.s, and is represented by General formula (1) Epoxy resin composition whose content of resin is 30 weight% or more with respect to the whole epoxy resin. In General formula (1), G is a glycidyl group, R <_1> , R <_3> is hydrogen or a hydrocarbon group, R <_2> is a substituent represented by Formula (a), n is 1-20, p represents 0.1-2.5 .

Description

Epoxy resin composition and hardened | cured material {EPOXY RESIN COMPOSITION AND CURED SUBSTANCE}

The present invention relates to an epoxy resin composition having excellent flame retardancy and imparting a cured product excellent in fluidity, curability and the like during molding, and a cured product thereof.

In recent years, especially with the advancement of the advanced material field, development of a higher performance base resin is calculated | required. For example, in the field of semiconductor encapsulation, the problem of a package crack is aggravated by the thinning of the package corresponding to the recent high density mounting, the large area, and the spread of the surface mounting method, and the base resin. There is a strong demand for improvement of moisture resistance, heat resistance, adhesiveness with a metal substrate, and the like. In addition, from the viewpoint of reducing the environmental load, there is a movement of eliminating halogen-based flame retardants, and a base resin excellent in flame retardancy is required.

However, it is not yet known in the conventional epoxy resin material to satisfy these requirements sufficiently. For example, well-known bisphenol-type epoxy resins are liquid at normal temperature and excellent in workability, but are widely used in terms of easy mixing with a curing agent, additives, and the like, but have problems in terms of heat resistance and moisture resistance. Moreover, although the phenol novolak-type epoxy resin is known as what improved heat resistance, there exists a problem in moisture resistance and impact resistance. In addition, Japanese Patent Laid-Open No. 63-238122 proposes an epoxy compound of phenol aralkyl resin for the purpose of improving moisture resistance and impact resistance, but it is not sufficient in terms of heat resistance and flame resistance.

As a method for improving flame retardancy without using a halogen flame retardant, a method of adding a phosphate ester flame retardant to JP-A-9-235449 and JP-A-10-182792 is disclosed. have. However, the method of using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, under high temperature and high humidity conditions, phosphate esters cause hydrolysis to deteriorate reliability as an insulating material.

Japanese Patent Laid-Open No. 11-140166 JP 2004-59792 A Japanese Patent Application Laid-Open No. 4-173831 Japanese Patent Laid-Open No. 2000-129092 Japanese Patent Laid-Open No. 3-90075 Japanese Patent Laid-Open No. 3-281623 Japanese Unexamined Patent Publication No. Hei 8-120039 Japanese Patent Application Laid-Open No. 5-140265

Patent Documents 1, 3, and 4 disclose an example in which an aralkyl type epoxy resin having a biphenyl structure is applied to a semiconductor encapsulating material without containing a phosphorus atom or a halogen atom and improving flame retardancy. Patent Document 2 discloses an example of using an aralkyl type epoxy resin having a naphthalene structure. However, these epoxy resins are not sufficient in either flame retardancy, moisture resistance or heat resistance. Further, Patent Documents 5 and 6 disclose naphthol-based aralkyl type epoxy resins and semiconductor encapsulating materials containing the same, but do not focus on flame retardancy. On the other hand, as an example focusing on the improvement of heat resistance, moisture resistance, and crack resistance, Patent Document 7 discloses a benzylated polyphenol and its epoxy resin, but these are not focused on flame retardancy. In addition, the benzylated polyphenol type epoxy resin has a problem in fluidity during molding due to the increase in molecular weight by benzylation. In addition, Patent Document 8 discloses an epoxy resin composition containing a styrenated phenol novolak-type epoxy resin, and is excellent in low water absorption and low stress, but is not focused on flame retardancy, and has sufficient performance in fluidity during molding. Not.

Accordingly, an object of the present invention is to secure flame retardancy in non-halogen, and to have excellent performance in fluidity, curability, and the like at the time of molding, and to use an epoxy resin composition and a cured product thereof useful for applications such as lamination, molding, molding, and adhesion. It is to offer.

That is, this invention is an epoxy resin composition containing an epoxy resin, a phenolic hardening | curing agent, and an inorganic filler, WHEREIN: The epoxy resin component is an amorphous epoxy resin represented by following General formula (1), and melt viscosity at 150 degreeC. Contains 0.001-0.05 Pa.s difunctional crystalline epoxy resin, and the content of the amorphous epoxy resin represented by the following general formula (1) is 30% by weight or more based on the whole epoxy resin, and is bifunctional crystal The epoxy resin composition is characterized in that the content of the epoxy resin is 30% by weight or more.

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

It is good that the said bifunctional crystalline epoxy resin component is an epoxy resin represented by following General formula (2).

(R ₄ to R ₁₁ may be selected from a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, and both may be the same or different. X is a single bond, -CH _2- , -C (CH ₃ ) ₂ -,- CO-, -O-, -S- or -SO _2- , G represents a glycidyl group, and m represents a number of 0-3.)

Moreover, it is good that the said hardening | curing agent component contains at least 1 sort (s) of an aralkyl type phenol type hardening | curing agent and a novolak-type phenol type hardening | curing agent.

Moreover, this invention relates to the epoxy resin composition which hardens the said epoxy resin composition whose content rate of an inorganic filler is 70 to 95 weight%, and these epoxy resin compositions.

According to the present invention, there is provided an epoxy resin composition which exhibits excellent fluidity and curability, exhibits excellent flame retardancy in a non-halogen system, and is useful for semiconductor encapsulation materials, molding materials, lamination materials, powder coating materials and adhesive materials.

The epoxy resin composition of this invention has two types of epoxy resin components, a phenolic hardening | curing agent component, and an inorganic filler as essential components. Advantageously, these essential ingredients comprise at least 50% by weight, preferably at least 80% by weight, more preferably at least 95% by weight.

First, the epoxy resin represented by General formula (1) which is the 1st type of epoxy resin component in the epoxy resin composition of this invention is demonstrated. The epoxy resin represented by this general formula (1) is an amorphous epoxy resin. The epoxy resin represented by General formula (1) is obtained by epoxidizing the styrene addition polyhydric hydroxy resin represented by General formula (3). In addition, the styrene addition polyhydric hydroxy resin (also called StPN) represented by General formula (3) adds the polyhydric hydroxy compound (also called polyvalent hydroxy compound (4)) and styrene represented by General formula (4). It can obtain by making it react.

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

(Wherein R ₁ represents hydrogen or a hydrocarbon group of 1 to 6 carbon atoms and n represents a number of 1 to 20).

The styrene-added polyhydric hydroxy resin represented by the general formula (3) can arbitrarily adjust the hydroxyl equivalent by adding styrene to the basic structure of the polyvalent hydroxy compound (4). Here, adding styrene means replacing the hydrogen of the benzene ring of the polyhydric hydroxy compound (4) and the substituent represented by Formula (a) (also called a styrenyl group). That is, in the epoxy resin hardened | cured material, although the hydroxypropyl group produced | generated by reaction of an epoxy group and a hydroxyl group is considered to be easy to burn, by increasing a hydroxyl equivalent, the aliphatic carbon ratio of the easily burnable component derived from an epoxy group becomes low, It can express a high degree of flame retardancy. Moreover, by adding styrene rich in aromaticity, aromaticity is further improved, and it is effective in improving flame resistance and moisture resistance.

Therefore, using these, a highly flame-retardant epoxy resin composition, especially the epoxy resin composition for semiconductor encapsulation, is obtained. That is, the physical properties excellent in high flame retardance, moisture resistance, and low elasticity are expressed with the outstanding curability in these compositions, and the sealing of electrical and electronic components, circuit board material, etc. with high reliability are obtained using this material.

StPN is obtained by addition-reacting polyvalent hydroxy compound (4) and styrene represented by General formula (4). At this time, considering the balance between the flame retardance and the curability of the cured product obtained as the ratio of the polyhydric hydroxy compound (4) and styrene, the use ratio of styrene to 1 mol of the polyhydric hydroxy compound is preferably in the range of 0.1 to 2.5 moles. More preferably, it is 0.1-1.0 mol, More preferably, it is the range of 0.3-0.8 mol. When less than this range, the property of the polyhydric hydroxy compound of a raw material is the state as it is not improved, and when more than this range, functional group density becomes too low and there exists a tendency for sclerosis | hardenability to fall.

In General formula (3) and General formula (1), common symbol has the same meaning. R ₁ represents a styrenyl group represented by the formula (a). p represents the number of 0.1-2.5, and this means the number (average number) of the average of the styrenyl group substituted by one phenol ring. p is preferable in order of 0.1-2 mol, 0.1-1.0 mol, 0.3-1 mol, 0.3-0.8 mol. In addition, up to 4 styrenyl groups can be substituted for the phenol ring at both terminals, and up to 3 styrenyl groups can be substituted for the intermediate phenol ring, and thus, when n is 1, up to 8 styrenyl groups can be substituted. .

From another viewpoint, it is preferable that the number of substitutions (number average) of the styrenyl group per molecule of StPN used for this invention is 1 or more, More preferably, it is 2 or more, More preferably, it is 2.6-4.

In formula (a), although R <_3> represents hydrogen or a C1-C6 hydrocarbon group, Preferably it is hydrogen or a C1-C3 alkyl group, More preferably, it is hydrogen. This R ₃ is determined by styrene used as a reaction raw material.

In General formula (1), although n shows the number of 1-20, Preferably it is the range of 1.5-5.0 as an average.

Next, the manufacturing method of StPN is demonstrated. The manufacturing method of StCN is performed by making 0.1-2.5 mol of styrene react with presence of an acid catalyst with respect to 1 mol of hydroxy groups of the polyhydric hydroxy compound represented by General formula (4). As a polyhydric hydroxy compound represented by General formula (4), a phenol novolak or a cresol novolak is typical. Although the usage-amount of styrene is 0.1-2.5 with respect to 1 mol of hydroxyl groups, 0.1-1.0 are preferable and 0.3-0.8 are more preferable.

The phenols used for obtaining the polyvalent hydroxy compound (4) are phenols substituted with phenol or a hydrocarbon group having 1 to 6 carbon atoms, preferably phenols substituted with phenol or alkyl groups having 1 to 4 carbon atoms, and more preferably. Is phenol. When phenol is used as phenols, a small amount of other phenol components may be included. For example, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydro Quinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol Etc. can be mentioned. These phenols or naphthols may include two or more kinds.

The styrenes used for the reaction with the polyvalent hydroxy compound are styrenes or styrenes substituted with a hydrocarbon group having 1 to 6 carbon atoms, preferably styrene. These styrenes may contain a small amount of other reaction components. When styrene is used as the styrenes, these styrenes may be used as other reaction components, such as α-methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole or vinyl naphthalene. An unsaturated bond containing component can be included, In this case, the polyhydric hydroxy compound obtained will contain the compound substituted by the aromatic ring in the group which arises from these.

Reaction with styrene with a polyhydric hydroxy compound can be performed in presence of an acid catalyst, The catalyst amount is used in 10-1000 ppm, Preferably it is 100-500 ppm. When more than this, the methylene crosslinking of a phenol novolak becomes easy to cleave, and the curable and heat resistance fall by the monovalent phenol component byproduced by a cleavage reaction. On the other hand, when less than this, reactivity will fall and many unreacted styrene monomer will remain.

As this acid catalyst, it can select from well-known inorganic acid and organic acid suitably. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, Lewis acids, such as boron trifluoride, or solid acids, such as an ion exchange resin, activated clay, silica-alumina, and zeolite, etc. are mentioned.

In addition, reaction temperature in this reaction is performed in 40-120 degreeC. If lower than this, reactivity will fall and reaction time will be long. Moreover, when it is higher than this, the methylene crosslinking of a phenol novolak becomes easy to partly cleave, and hardenability and heat resistance fall by the monovalent phenol component byproduced by a cleavage reaction.

In addition, this reaction is normally performed for 1 to 20 hours. In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethyl ether, diethyl ether, Ethers, such as diisopropyl ether, tetrahydrofuran, and dioxane, aromatic compounds, such as benzene, toluene, chlorobenzene, and dichlorobenzene, etc. can be used as a solvent.

As a specific method of carrying out this reaction, all the raw materials are charged in a batch and reacted as they are at a predetermined temperature, or a polyvalent hydroxy compound and a catalyst are charged and reacted while dropping styrene while maintaining at a predetermined temperature. The method is common. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. In the case of using a solvent after the reaction, the catalyst component is removed if necessary, and then the solvent is distilled off to obtain a resin for use in the present invention. Can be obtained.

The epoxy resin used for this invention is an epoxy resin represented by the said General formula (1), and bifunctional crystalline epoxy resin whose melt viscosity in 150 degreeC is 0.001-0.05 Pa.s.

Hereinafter, the epoxy resin represented by General formula (1) is abbreviated as StPNE, and the bifunctional crystalline epoxy resin whose melt viscosity in 150 degreeC is 0.001-0.05 Pa.s may be called crystalline epoxy resin. StPNE can be obtained by epoxidizing the StPN.

In General formula (1), the symbol common with General formula (3) has the same meaning, G represents a glycidyl group and this arises by reaction of the hydroxyl group of General formula (3). R ₁ is a styrenyl group.

Although StPNE used for this invention is manufactured by making StPN represented by the said General formula (3), and epichlorohydrin react, it is not limited to this reaction.

In addition to the reaction of reacting StPN with epichlorohydrin, a method of reacting StPN with allyl halide to form an allyl ether compound and then reacting with a peroxide may be employed. Reaction which makes said StPN react with epichlorohydrin can be performed similarly to normal epoxidation reaction.

For example, after dissolving the StPN in excess epichlorohydrin, in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, the reaction is at 20 to 150 ° C, preferably at 30 to 80 ° C for 1 to 10 hours. The method of making it come is mentioned. The usage-amount of the alkali metal hydroxide at this time is 0.8-1.5 mol with respect to 1 mol of hydroxyl groups of StPN, Preferably it is the range of 0.9-1.2 mol. 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, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off. Epoxy resin can be obtained.

The epoxy resin composition of this invention contains 30 weight% or more, Preferably it is 30-70 weight%, More preferably, 40-60 weight% of the epoxy resin represented by the said General formula (1) in all the epoxy resin components. do.

The epoxy resin composition of this invention is 30 weight% or more, Preferably, as a 2nd type epoxy component, bifunctional crystalline epoxy resin whose melt viscosity in 150 degreeC is 0.001-0.05 Pa.s in all the epoxy resin components. Is 30 to 70% by weight, more preferably 40 to 60% by weight. If more than this, flame retardancy will fall, and if it is less than this, the fluidity | liquidity at the time of shaping | molding made into the objective of this invention will not fully express.

The melt viscosity at 150 degreeC of the said bifunctional crystalline epoxy resin is 0.001-0.05 Pa * s, Preferably it is 0.005-0.03 Pa * s. When the melt viscosity is higher than 0.05 Pa · s, it is difficult to increase the high filling rate of the inorganic filler, and improvement in performance such as flame retardancy cannot be expected.

As a bifunctional crystalline epoxy resin, the epoxy resin shown by the said General formula (2) is used preferably. In General formula (2), R <_4> -R <_11> is chosen from a hydrogen atom and a C1-C6 hydrocarbon group, Preferably it is a hydrogen atom or a C1-C6 alkyl group. These may all be the same or different. X represents a single bond, -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- . G represents a glycidyl group. Although m represents the number of 0-3, when m is resin which consists of several other components, m shows the number average value.

Preferably, epoxy resins as shown in the following general formulas (5) to (14) are used. In formula, R <_4> -R <_11> is chosen from a hydrogen atom and a C1-C6 hydrocarbon group, and all may be same or different. G represents a glycidyl group, and m represents the number of 0-3.

The bifunctional crystalline epoxy resins may be used alone or in combination of two or more thereof. Among these epoxy resins, it is particularly preferable to use a biphenyl type epoxy resin, a bisphenol F type epoxy resin and a sulfide type epoxy resin in view of both fluidity and flame retardancy.

Said bifunctional crystalline epoxy resin can be synthesize | combined by making epichlorohydrin react with the compound which has a phenolic hydroxyl group represented by a bisphenol compound. This reaction can be performed similarly to a normal epoxidation reaction. In the case of using a bisphenol compound, for example, the bisphenol compound is dissolved in excess epichlorohydrin, and then, in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, 50 to 150 ° C, preferably 60 to 120 ° C. The method of making it react for 10 hours is mentioned. At this time, the usage-amount of an alkali metal hydroxide is 0.8-2 mol, Preferably it is 0.9-1.2 mol with respect to 1 mol of hydroxyl groups of a bisphenol compound. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off. Epoxy resin can be used.

The amount of hydrolyzable chlorine of the epoxy resin used for this invention is good from a viewpoint of the reliability improvement of the electronic component to seal. Although it does not specifically limit, 1000 ppm or less is preferable, More preferably, it is 500 ppm or less. In addition, the hydrolysable chlorine used by this invention means the value measured by the following method. That is, 0.5 g of a sample was dissolved in 30 ml of dioxane, 10 ml of 1N-KOH was added thereto, and the mixture was refluxed for 30 minutes. After cooling to room temperature, 100 ml of 80% acetone water was added, followed by 0.002N-AgNO ₃ It is the value obtained by performing potential difference titration with aqueous solution.

Although the epoxy resin composition of this invention uses an epoxy resin represented by the said General formula (1) and a bifunctional crystalline epoxy resin as an essential epoxy resin as an epoxy resin component, in the range which does not impair the objective of this invention. Another epoxy resin can also be used together.

Examples of such other epoxy resins include epoxides of dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, resorcin, and naphthalenediol. Epoxy of trivalent or more phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak A biphenyl aralkyl type synthesize | combined from the cargo, the epoxide of the co-condensation resin of dicyclopentadiene, and phenols, the epoxide of phenol aralkyl resins synthesize | combined from phenols and paraxylylenedichloride, phenols, bischloromethyl biphenyl, etc. Epoxides of phenol resins, epoxides of naphthol aralkyl resins synthesized from naphthols and paraxylylenedichloride, and the like. These epoxy resins may be individual and may use 2 or more types together. Although these compounding quantities should just be a range which does not impair the objective of this invention, it is less than 50 weight% with respect to the total of StPNE and a bifunctional crystalline epoxy resin.

Specific examples of the phenolic curing agent used in the epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, Divalent phenols such as resorcin, catechol, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o -Trihydric or higher phenols represented by cresol novolac, naphthol novolak, polyvinylphenol, or the like, and also phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2, Divalent phenols such as 2'-biphenol, hydroquinone, resorcin, catechol, naphthalenediol, formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene Glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyl There may be mentioned divinyl biphenyl, diisopropenyl biphenyls polyhydric phenolic compound, which is synthesized by the reaction of the crosslinking agent and the like.

Preferably the softening point range of a phenolic hardening | curing agent is 40-150 degreeC, More preferably, it is 50-120 degreeC. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in mixing kneading property and moldability in preparing an epoxy resin composition. Moreover, melt viscosity in preferable 150 degreeC is 1 Pa * s or less, More preferably, it is 0.5 Pa * s or less. If it is higher than this, there is a problem in mixing kneading property and moldability in preparing the epoxy resin composition.

In the epoxy resin composition of this invention, it is preferable that the compounding ratio of an epoxy resin and a hardening | curing agent is the range of 0.8-1.5 in an equivalence ratio of the functional group in an epoxy group and a hardening | curing agent. Outside this range, unreacted epoxy group or functional group in a hardening | curing agent remains after hardening, and physical properties, such as reliability, water absorption, etc. at the time of making hardened | cured material fall.

Examples of the inorganic filler used in the present invention include silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, mullite, titania, and the like. Although these 1 type (s) or 2 or more types may be combined, it is preferable to have fused silica as a main component, and the crushed or spherical thing is mentioned as the form. Usually, silica is used combining what has several types of particle size distributions. As for the range of the average particle diameter of the silica to combine, 0.5-100 micrometers is good. Although the content rate of an inorganic filler is good in the range of 70 to 95 weight%, Preferably it is 80 to 95 weight%, More preferably, it is 85 to 95 weight%. When smaller than this, the content rate of an organic component becomes high and a flame retardance is not fully exhibited. On the contrary, when it becomes larger than this, the thermal conductivity of a molded article will become large, and the decomposition rate of an organic component will become high, and the formation amount of a heat insulation carbonization layer will become small, and it will become difficult to exhibit flame retardance.

Moreover, in the epoxy resin composition of this invention, you may mix suitably oligomers and high molecular compounds, such as polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, an indencoumarone resin, a phenoxy resin, as needed, You may mix | blend additives, such as a pigment, a flame retardant, a thixotropic agent, a coupling agent, and a fluidity improving agent. Examples of the pigment include organic or inorganic extender pigments and scale pigment pigments. Examples of the thixotropic agent include silicone type, castor oil type, aliphatic amide wax, polyethylene oxide wax, organic bentonite type and the like. Moreover, you may mix | blend hardening accelerators, such as amines, imidazole, organic phosphine, and Lewis acid, as needed. As a compounding quantity, it is 0.2-5 weight part with respect to 100 weight part of epoxy resins normally. Furthermore, if necessary, the resin composition of the present invention may be a release agent such as carnauba wax, OP wax, coupling agent such as γ-glycidoxypropyltrimethoxysilane, colorant such as carbon black, flame retardant such as antimony trioxide, Low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be blended.

The hardened | cured material of this invention can be obtained by hardening the said epoxy resin composition by shaping | molding methods, such as casting, compression molding, and transfer molding. The temperature at the time of hardened | cured material formation is 120-220 degreeC normally.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely based on a synthesis example, an Example, and a comparative example.

(Synthesis of Polyhydroxy Resin)

(Synthesis Example 1)

In a 1 L four-necked flask, a phenol novolak (Showa Polymer Products; BRG-555, hydroxyl equivalent 105 g / eq., Softening point 67 DEG C, 150 DEG C, melt viscosity 0.08 Pa.s) as a polyhydric hydroxy compound component ) Was charged with 105 g of toluene, 5.3 g of toluene, and 0.055 g (300 ppm) of p-toluenesulfonic acid as the acid catalyst, and the temperature was raised to 100 ° C. Next, while stirring at 100 degreeC, 73 g (0.7 mol) of styrene was dripped for 3 hours, and it was made to react. Furthermore, after 2 hours of reaction at 100 ° C, 0.049 g of 30% Na ₂ CO ₃ was added to neutralize. Next, it dissolved in 330 g of MIBK and washed with water five times at 80 degreeC. Subsequently, 170 g of polyhydric hydroxy resins were obtained after distilling off MIBK under reduced pressure. As for the hydroxyl equivalent, 178 g / eq., The softening point were 78 degreeC, and melt viscosity in 150 degreeC was 0.13 Pa.s. This resin is called StPN-A.

(Synthesis Example 2)

(Synthesis of epoxy resin)

150 g of StPN-A obtained in Synthesis Example 1, 468 g of epichlorohydrin and 70 g of diethylene glycol dimethyl ether were added to a four-neck separable flask, and the mixture was stirred. After homogeneous dissolution, the mixture was maintained at 65 ° C. under reduced pressure of 130 mmHg, and 70.3 g of 48% aqueous sodium hydroxide solution was added dropwise for 4 hours. Epichlorohydrin was returned to the reaction vessel, and water was removed to react with the system. After completion | finish of reaction, the salt produced | generated by filtration was removed, and after further washing with water, epichlorohydrin was distilled off and 185g of epoxy resins were obtained (StPNE-A). As for epoxy equivalent of obtained resin, melt viscosity in 56 degreeC and 150 degreeC of 246g / eq. And softening point was 0.10 Pa.s.

(Examples 1-4, Comparative Examples 1-3)

The epoxy resin (StPNE-A) obtained by the said synthesis example 2, the epoxy resin shown below, a hardening | curing agent, triphenylphosphine as an inorganic filler, and a hardening accelerator, and other additives are mixed by the compounding ratio shown to Tables 1-2. Kneading to prepare an epoxy resin composition. The numerical value in a table | surface shows a weight part in mix | blending.

Epoxy resin A: 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl (YX4000H; epoxy equivalent 195, melting point 105 ° C, 150) as a bifunctional crystalline epoxy resin Melt viscosity at 1 ° C. 0.011 Pa · s, manufactured by Mitsubishi Chemical Corporation), Epoxy Resin B: Epoxide of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane (YSLV- 80XY: epoxy equivalent 193, melting point 78 ° C., melt viscosity 0.008 Pa · s at 150 ° C., manufactured by Shinnitetsu Chemical Co., Ltd.). Moreover, epoxy resin C: o-cresol novolak-type epoxy resin (epoxy equivalent 200, softening point 65 degreeC, the Shin-Nitetsu Chemical Co., Ltd. product) was used as a comparative epoxy resin.

Phenol aralkyl resin (PA; MEH-7800SS (made by Meiwa Kasei), OH equivalent 175, softening point 67 degreeC) or phenol novolak (PN; PSM-4261 (made by Gunei Chemical), OH equivalent 103 as a hardening | curing agent component , Softening point 82 ° C.) was used.

After molding at 175 ° C using this epoxy resin composition, and postcure at 175 ° C for 12 hours to obtain a cured product test piece, it was used for measuring various physical properties. The results are shown in Tables 3-4.

1) Measurement of epoxy equivalent

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

2) Softening point

It measured by the circular ball method according to JIS-K-2207 using the automatic softening point apparatus (ASP-M4SP by Meihosha Seisakusho Co., Ltd.).

3) Melt viscosity

It measured at 150 degreeC using the Brookfield-made CAP2000H type | mold rotational viscometer.

4) gel time

Epoxy resin composition was added to the plate of the gelling tester (made by Nisshin Chemical Co., Ltd.) heated at 175 degreeC, and it stirred at the speed of 2 rotations for 1 second using a fluororesin rod, and the epoxy resin composition The required gelation time was investigated until curing.

5) spiral flow

For spiral flow, the epoxy resin composition is molded under the conditions of injection pressure (150Kgf / cm ² ) and curing time of 3 minutes using a spiral flow measuring mold according to the standard (EMMI-1-66), and the flow length is adjusted. Investigate.

6) Line expansion coefficient (CTE), glass transition point (Tg)

With the Seiko Instruments TMA120C type thermomechanical measuring device, Tg is calculated | required on the conditions of a temperature increase rate of 10 degree-C / min, and (alpha) 1 (Tg or less CTE) is an average value of the range of 30-50 degreeC, and α2 (CTE more than Tg) ) Was obtained from an average value in the range of Tg plus 20 ° C to 40 ° C.

7) bending strength and bending elasticity

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

8) adhesive strength

The molded product of 25 mm x 12.5 mm x 0.5 mm was formed at 175 degreeC by the compression molding machine between two copper plates, and after performing postcure at 180 degreeC for 12 hours, it evaluated by obtaining the tensile shear strength. It was.

9) Absorption rate

The conditions of 25 degreeC and 50% of the relative humidity were made into the standard state, and it was set as the weight change rate after moisture-absorbing for 100 hours on 85 degreeC and the conditions of 85% of the relative humidity.

10) Flame retardant

A test piece having a thickness of 1/16 inch was molded, evaluated by the UL94V-0 standard, and represented by the total combustion time in the five test pieces.

The epoxy resin composition of the present invention provides a cured product excellent in fluidity and curability, and excellent in flame retardancy, moisture resistance and low elasticity, and can be suitably used for applications such as sealing of electrical and electronic components, circuit board materials and the like. In particular, while excellent in fluidity and flame retardancy, and ensuring excellent moldability, the use of environmentally loaded flame retardants is unnecessary or reduced.

Claims (5)

Epoxy resin composition containing epoxy resin, a phenolic hardening | curing agent, and an inorganic filler WHEREIN: The epoxy resin component is 0.001-0.05 Pa of amorphous epoxy resin represented by following General formula (1), and melt viscosity in 150 degreeC. The content of the amorphous epoxy resin represented by the following general formula (1) is 30% by weight or more, and the content of the bifunctional crystalline epoxy resin is contained in the difunctional crystalline epoxy resin which is s. Epoxy resin composition, characterized in that more than 30% by weight.

Here, 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 following formula (a), and n represents a number of 1 to 20. In addition, p represents the number of 0.1-2.5.

Here, R <_3> represents hydrogen or a C1-C6 hydrocarbon group. The method of claim 1,
An epoxy resin composition, wherein the bifunctional crystalline epoxy resin component is an epoxy resin represented by the following General Formula (2).

Here, R <_4> -R <_11> is chosen from hydrogen and a C1-C6 hydrocarbon group, and all may be same or different. X represents a single bond, -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- . G represents a glycidyl group, and m represents the number of 0-3. The method of claim 1,
Epoxy resin composition, characterized in that the phenolic curing agent component contains at least one selected from aralkyl type phenolic curing agent and novolak type phenolic curing agent. The method of claim 1,
Epoxy resin composition, characterized in that the content of the inorganic filler is 70 to 95% by weight. Hardened | cured epoxy resin formed by hardening | curing the epoxy resin composition in any one of Claims 1-4.