TW201229122A - Epoxy resin composition and cured substance - Google Patents

Abstract

An epoxy resin composition that exhibits excellent fluidity, hardens well, exhibits excellent flame retardancy for a non-halogen resin, and is useful as a semiconductor sealant, molding material, lamination material, powder coating, adhesive material, or the like. The epoxy resin component of said epoxy resin composition contains an epoxy resin represented by general formula (1) and a bifunctional crystalline epoxy resin having a melt viscosity of 0.001-0.05 Pas at 150 DEG C, with the weight of the epoxy resin represented by general formula (1) being at least 30% of that of the entire epoxy resin. In general formula (1), G represents a glycidyl group, R1 and R3 represent hydrogen or hydrocarbon groups, R2 represents a substituent represented by formula (a), n represents 1 to 20, and p represents 0.1 to 2.5.

Description

[Technical Field] The present invention relates to an epoxy resin composition and a cured product thereof which are excellent in flame resistance and are excellent in fluidity and hardenability at the time of molding. [Prior Art] In recent years, in particular, with the advancement of advanced materials, development of a substrate resin of higher performance has been sought. For example, in the field of semiconductor packaging, it is thinner and larger in size than the package of high-density packaging in recent years, and the problem of cracking of the package is most serious with the spread of surface mounting methods. In the resin, it is strongly sought to improve moisture resistance, heat resistance, adhesion to a metal substrate, and the like. Further, from the viewpoint of reducing the environmental load, a substrate resin having a function of eliminating a halogen-based flame retardant and having excellent flame resistance is sought. However, those who fully satisfy these requirements in the conventional epoxy resin materials are not known. For example, the known bisphenol type epoxy resin is widely used in the form of a liquid at room temperature, and is excellent in workability or blending with a curing agent or an additive. However, it is widely used in heat resistance and moisture resistance. problem. Further, in the case of improving heat resistance, a phenol novolac type epoxy resin is known, but there is a problem in moisture resistance and impact resistance. Further, in JP-A-63-23 8 1 22, an object is to improve the moisture resistance and impact resistance, and to propose an epoxy compound of a phenol aralkyl resin, but the point of heat resistance or flame resistance is not full. A method for adding a phosphate-based flame retardant has been disclosed in the Japanese Patent Laid-Open No. Hei 9-235449, No. Hei 10-182792, and the like, and a method for improving the flame resistance of a halogen-based flame retardant. . However, the method using a phosphate-based flame retardant is insufficient in moisture resistance. Further, in the high-temperature and high-humidity environment, the phosphate ester is hydrolyzed, and there is a problem that the reliability of the insulating material is lowered. [Prior Art Document] [Patent Document 1] [Open Patent Document 2] Special Opening [Patent Document 3] Special Opening [Patent Document 4] Special Opening [Patent Document 5] Special Opening [Patent Document 6] Special Opening [Patent Literature] [Patent Document 8] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei 5-140265 discloses an aralkyl type epoxy resin having a biphenyl structure as disclosed in Patent Documents 1, 3 and 4 in the case of not containing a phosphorus atom or a halogen atom and improving flame resistance. In the case of semiconductor packaging materials. An example of using an aralkyl type epoxy resin having a naphthalene structure has been disclosed in Patent Document 2. However, these epoxy resins are insufficient in performance in any of flame resistance, moisture resistance, and heat resistance. Further, in Patent Documents 5 and 6, a naphthol aralkyl type epoxy resin and a semiconductor encapsulating material containing the same have been disclosed, but the flame resistance is not focused. Further, in the case of focusing on the improvement of heat resistance, moisture resistance, and crack resistance, Patent Document 7 discloses that benzene S. -6- 201229122 methylated polyacid and epoxy thereof have been disclosed. Resin' but these are not aimed at the flame resistance. Further, the benzylated polyether epoxy resin has a problem in fluidity at the time of molding due to an increase in the molecular weight of benzylation. Further, Patent Document 8 discloses an epoxy resin composition containing a styrenated acid phthalic acid-type resin, which is excellent in low water absorption and low stress, but does not focus on flame resistance and fluidity at the time of molding. Insufficient performance. [Disclosure of the Invention] Accordingly, it is an object of the present invention to provide a property of ensuring non-halogen flame resistance while having excellent fluidity, hardenability, and the like in forming, and can be used for lamination, forming, and pouring. And the epoxy resin composition and its hardened material for the purpose of use. That is, the present invention relates to an epoxy resin composition which is contained in an epoxy resin composition containing an epoxy resin, a phenolic curing agent, and an inorganic cerium material, and the epoxy resin component contains the following general formula. (1) the non-knot shown

The crystalline epoxy resin and the difunctional crystalline epoxy resin having a melt viscosity of 0.001 to 0.05 Pa·s at 150 t are amorphous as shown in the following general formula (1) with respect to the entire epoxy resin. The content of the epoxy resin is 3 〇 wt% or more, and the content of the difunctional crystalline epoxy resin is 30% by weight or more;

-7- 201229122 【化2】

I HC-CH, ^ Μ r3 (In the formula (1), G represents a glycidyl group] R1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and R2 represents a substituent represented by the following formula (a) , η represents a number from 1 to 20; further, ρ represents a number from 0.1 to 2.5; in the formula ("R3 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 6). It may also be an epoxy resin composition, wherein The bifunctional crystalline epoxy resin component is an epoxy resin represented by the following formula (2):

OG (2) (wherein R4-RH is selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 6 carbon atoms) may be the same or different; X represents a single bond, -匚112-, -(:((^ 3) 2-, -CO-, -〇·, -S - or - S02-; G represents a glycidyl group 'm represents the number of 〇~3). Further, the above-mentioned hardener component may also contain an aralkyl group At least one of a phenolic curing agent and a novolak-type phenolic curing agent. Further, the present invention relates to an epoxy resin composition having a content of an inorganic cerium filling material of 70 to 95% by weight, and the like. An epoxy resin cured product obtained by hardening an epoxy resin composition.

S 201229122 [Formation for Carrying Out the Invention] The epoxy resin composition of the present invention contains two types of epoxy resin components, a phenolic curing agent component, and an inorganic cerium filler as essential components. It is preferable to contain 50% by weight or more of the essential components, preferably 80% by weight or more, and more preferably 95% by weight or more. First, an epoxy resin represented by the formula (1) relating to the first type of epoxy resin component in the epoxy resin composition of the present invention will be described. The epoxy resin represented by the above formula (1) is an amorphous epoxy resin. The epoxy resin represented by the formula (1) can be obtained by epoxidation of a styrene-added polyvalent hydroxy resin represented by the formula (3). Further, the styrene-added polyvalent hydroxy resin (also referred to as StPN) represented by the formula (3) can be a polyvalent hydroxy compound represented by the formula (4) (also referred to as a polyvalent hydroxy compound). (4)) obtained by addition reaction with styrene. 【化4】

(Ri is a hydrogen group or a hydrocarbon group having 1 to 6 carbon atoms, R 2 is a substituent represented by the above formula (a), and η is a number of 0 to 2 0; and p is a number of 0.1 to 2.5. -9- (4) (4)201229122 η (where 'Ri represents hydrogen or carbon number! ~6 hydrocarbon group, η represents 1~20) styrene represented by formula (3) The addition of the polyvalent hydroxy resin firstly allows the hydroxyl equivalent to be arbitrarily adjusted by adding benzene to the basic structure of the polyvalent hydroxy compound (4). Here, the so-called addition styrene system makes multivalent The hydrogen of the benzene ring of the hydroxy compound (4) is substituted with a substituent represented by the formula (a) (also referred to as a styryl group), that is, the epoxy group and the hydroxyl group are reacted in the hardened epoxy resin. The resulting hydroxypropyl group forms a flammable portion. However, the aliphatic carbon ratio of the flammable component derived from the epoxy group is lowered to improve the flammability of the epoxy group, and the flame resistance is high. Further, it is rich in aromatics by addition. The styrene's aromaticity system is further improved, in addition to the improvement of flame resistance and moisture resistance. Therefore, high flame resistance can be obtained by using this. An epoxy resin composition, in particular, an epoxy resin composition for semiconductor encapsulation, that is, an excellent hardenability which is exhibited in a composition thereof, and is excellent in high flame resistance, moisture resistance, or low elasticity. The physical properties of the electric and electronic parts and the circuit board materials which are highly reliable can be obtained by using this material.

The StPN system can be obtained by subjecting a polyvalent hydroxy compound (4) represented by the formula (4) to a styrene addition reaction. At this time, the ratio of the polyvalent hydroxyl compound (4) to the styrene is considered to be resistant to the cured product obtained.

S -10- 201229122 The balance between flammability and hardenability, the ratio of styrene to polyvalent hydroxy compound 1 mole is preferably in the range of 0.1 to 2.5 moles, more preferably 0.1 to 1.0 moles, most preferably 0.3. ~0.8 mole range. When the amount is less than this range, the properties of the polyvalent hydroxy compound which is a raw material are not directly improved, and when it is more than this range, the functional group density tends to be too low and the hardenability tends to be lowered. In the general formula (3) and the general formula (1), the common symbols have the same meaning. R represents a styryl group represented by the above formula (a). p represents the number of 0.1 to 2.5, but this means the average number (number average) of the styryl groups substituted into one phenol ring. Preferably, p is 0.1 to 2 moles, 0.1 to 1.0 moles, 0. 3 to 1 moles, and 0.3 to 0.8 moles. Further, the styrene group having a maximum of four phenol ring groups at both terminals may be substituted, and the maximum styrene group of the phenol ring system at the two ends may be substituted, so that a maximum of eight styryl groups may be substituted when η is 1. . From another viewpoint, the number of substitutions (number average) of styrene per molecule of the StPN system used in the present invention is preferably 1 or more, more preferably 2 or more, and most preferably 2.6 to 4. In the formula (a), R3 represents a hydrocarbon group of hydrogen or carbon number, but is preferably an alkyl group of hydrogen or a carbon number, more preferably hydrogen. this! The ^3 system may be determined according to the styrene used as a reaction raw material. In the formula (1), η represents the number of the oxime 20, but is preferably in the range of from 1-5 to 5.0. Next, explain the manufacturing method of StPN. The manufacturing method of StCN is carried out by reacting a hydroxy group of a polyvalent hydroxy compound represented by the formula (4) with a benzene ketone of 0.1 to 2.5 moles in the presence of an acid catalyst. (4) The polyvalent hydroxy compound shown is a phenol novolak or

S -11 - 201229122 Cresol novolac varnish is representative. The amount of the styrene used is 0.1 to 2.5', but preferably 01 to 1 (), more preferably 〇3 to 0.8, based on the hydroxyl group. The phenol used for obtaining the polyvalent hydroxy compound (4) is a phenol substituted with a phenol or a hydrocarbon group having 1 to 6 carbon atoms, but is preferably a phenol substituted with a phenol or an alkyl group having 1 to 4 carbon atoms. More suitable for phenol. When a phenol is used as a phenol, a small amount of a phenol component may be contained. For example, o-cresol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, tert-butyl phenol, allyl phenol, phenyl phenol, 2,6-dimethyl Phenol, 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 also contain two or more types. The styrene used for the reaction with the polyvalent hydroxy compound is styrene or a styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms, but is preferably styrene. The styrene system may also contain a small amount of other reaction components. When styrene is used, the other reaction components may contain α-methylstyrene, diethylbenzene, hydrazine, coumarin, and benzene. Further, a component containing an unsaturated bond such as thiophene, anthracene or vinylnaphthalene, in which case, the obtained polyvalent hydroxy compound contains a compound substituted on the aromatic ring derived therefrom. The reaction with the styrene of the polyvalent hydroxy compound can be carried out in the presence of an acid catalyst, and the amount of the catalyst is in the range of from 10 to 500 ppm. If it is more than this, the styrene crosslink bond of the phenol novolak is easily cleaved, and the monovalent phenol component produced by the cleaving reaction is lowered to lower the hardenability and heat resistance. Further, if less than this, the reactivity is lowered, and many unreacted styrene monomers remain.

S -12- 201229122 This acid catalyst can be suitably selected from known inorganic acids and organic acids. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as capric acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, and diethylsulfuric acid, or zinc chloride or aluminum chloride. A solid acid such as Lewis acid or ion exchange resin such as ferric chloride or boron trifluoride, activated clay, cerium oxide-alumina or zeolite. Further, the reaction temperature in this reaction is carried out in the range of 40 to 120 °C. If it is less than this, the reactivity is lowered and the reaction time becomes long. Further, if it is higher than this, the styrene crosslink bond of the phenol novolak is likely to be partially cleaved, and the monovalent phenol component formed by the reaction is cleaved to lower the hardenability and heat resistance. Further, the reaction is generally carried out for 1 to 20 hours. Further, in the reaction, an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve, or acetone, methyl ethyl ketone or methyl isobutyl ketone may be used. An ether such as a ketone, dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran or dioxane, or an aromatic compound such as benzene, toluene, chlorobenzene or dichlorobenzene is used as a solvent. The specific method for carrying out the reaction is generally carried out by charging the entire raw material at a time, directly reacting at a specific temperature, or placing a polyvalent hydroxy compound and a catalyst, maintaining the temperature at a specific temperature, and dropping the styrene while reacting. At this time, the dropping time is preferably 5 hours or less, and is usually 1 to 10 hours. After the reaction, when the solvent is used, if necessary, the catalyst component is removed, and the solvent is distilled off to obtain the resin used in the present invention. When the solvent is not used, the target product is obtained by direct heat discharge. The epoxy resin used in the present invention is a di-functional crystalline epoxy resin having a -13 to 201229122 epoxy resin represented by the above formula (1) and a melt viscosity at 150 ° C of 0.001 to 0.05 Pa·s. Hereinafter, the epoxy resin represented by the general formula (1) may be simply referred to as StPNE, and the difunctional crystalline epoxy resin having a melt viscosity at 150 ° C of 0.001 to 0.05 Pa·s may be simply referred to as a crystalline epoxy resin. . StPNE can be obtained by epoxidizing the above StPN. In the formula (1), the symbols common to the formula (3) have the same meaning, but G represents a glycidyl group, and the hydroxyl group of the formula (3) reacts to produce "R!" as a styryl group. The StPNE system used in the present invention is advantageously produced by reacting StPN represented by the above formula (3) with epichlorohydrin, but is not limited to this reaction. In addition to the reaction of reacting StPN with epichlorohydrin, a method in which StPN is reacted with a halogenated alkene group to form an allyl ether compound and then reacted with a peroxide may be employed. The reaction of reacting the above StPN with epichlorohydrin can be carried out in the same manner as in the general epoxy group reaction. For example, the StPN is dissolved in excess epichlorohydrin, and in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, it is 20 to 150 ° C, preferably 30 to 80 ° C. The range of reactions is 1 to 10 hours. The amount of the alkali metal hydroxide used at this time is in the range of 0.8 to 1.5 moles, preferably 〇·9 to 1.2 moles, relative to the hydroxyl group 1 mole of StPN. Further, epichlorohydrin is excessively used in comparison with the hydroxyl group 1 in StPN, but is generally 1.5 to 30 moles, preferably 2 to 15 moles, per mole of hydroxyl group 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, and washed with water to remove the inorganic salt.

S -14- 201229122 with a medium part of the fat. The formation of the resin oxygen tree epoxy full-ring system into the lipo-aerobic' ring of the solvent to the distillate after the general description of the above is recommended to the amount of weight ο 3 fatty tree oxygen ring The weight % is more preferably 40 to 60% by weight. The epoxy resin composition of the present invention contains a difunctional crystalline epoxy resin having a melt viscosity of 0.001 to 0.05 Pa·s at 150 t: for the epoxy resin component of the second type. 30% by weight or more' is preferably 30 to 70% by weight, more preferably 40 to 60% by weight. If it is more than this, the flame resistance is lowered, and if it is less than this, the fluidity at the time of molding of the object of the present invention is not sufficiently exhibited. 1 50 of the above difunctional crystalline epoxy resin. The melt viscosity in (: 0.001 to 0.05 Pa·s, preferably 0.005 to 0.03 Pa. s. If the melt viscosity is higher than 0.05 Pa. S, the high enthalpy of the inorganic ruthenium is difficult to change, and flame resistance is not expected. For the difunctional crystalline epoxy resin, the epoxy resin represented by the above formula (2) is preferably used. In the formula (2), here, R4 to Ri 1 are hydrogen. The atom and the hydrocarbon group having 1 to 6 carbon atoms are selected, but are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These systems may all be the same or different. The X system represents a single bond, -CH2- , -C ( CH3) 2-, -CO-, -0-, -S- or -S〇2_. G represents glycidyl group. m represents the number of 0~3, but m is composed of different complex components. In the case of the resin to be formed, m represents the number average 値. It is preferred to use an epoxy resin as shown in the following general formulae (5) to (14), wherein R4 to RM are hydrogen atoms and carbon. The number of hydrocarbon groups of 1 to 6 may be selected as 'all may be the same'. G represents a glycidyl group, and m is -15-201229122 shows the number of 〇~3.

(5)

(6)

(7)

GO

OG (8)

(9) -16- s 201229122 【化7】

The difunctional crystalline epoxy resin may be used alone or in combination of two or more. Among these epoxy resins, a biphenyl type epoxy resin, a bisphenol F type epoxy resin, and a thioether type epoxy resin are particularly preferable from the viewpoints of fluidity and flame resistance. The difunctional crystalline epoxy resin as described above can be synthesized by reacting a compound having a phenolic hydroxyl group typified by a bisphenol compound with epichlorohydrin. This reaction can be carried out in the same manner as a general epoxy group reaction. When the bisphenol compound is used, for example, the bisphenol compound is dissolved in excess epichlorohydrin, and then 50 to 150 in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. (:, it is preferable to react at 60 to 120 ° C for 1 to 10 hours. At this time, the amount of alkali metal hydroxide used is relative to the hydroxyl group of the bisphenol compound 1 - 17 29 22 122 ' ear 0.8 to 2 The ear 'should be 〇·9~ 1.2 mol. After the reaction is finished, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, and washed to remove the inorganic salt. The solvent is distilled off to form a desired epoxy resin. The amount of the hydrolyzable chlorine used in the epoxy resin of the present invention is preferably from the viewpoint of improving the reliability of the packaged electronic component, and is not particularly limited, but is preferably It is more preferably 100 ppm or less, and more preferably 500 ppm or less. Further, the hydrolyzable chlorine in the present invention is measured by the following method. That is, after the sample 〇 5 g is dissolved in 30 ml of the two chewing compound, IN - KOH is added. 10 ml, boiled and refluxed for 30 minutes, cooled to room temperature, and further, 100 ml of 8% acetone water was added, and potentiometric titration was carried out with a 〇.2N-AgNCh aqueous solution to obtain a ruthenium. For the epoxy resin component, the system is used as described above. The epoxy resin represented by the formula (1) and the difunctional crystalline epoxy resin are optional epoxy resins, but other epoxy resins may be used without departing from the object of the present invention. Examples of the resin include bisphenol bismuth epoxides such as bisphenol A, bisphenol F, biguanide S, bismuth bisphenol, 2,2,-biphenol, resorcin, and naphthalene glycol. Those showing crystallinity are removed), tris-(4-diphenylphenyl)methane, 1,;,2,2-tetrakis(4-hydroxyphenyl)ethane, phenolic varnish, o-cresol novolac An epoxide of a trivalent or higher phenolic epoxide I' dicyclopentadiene and a phenolic co-condensation resin, and a phenolic aralkyl synthesized from a phenol and a Z: chlorinated paraxylene An epoxide of a base resin, a biphenyl aralkyl type synthesized from a phenol and a bischloromethylbiphenyl group

-18- S 201229122 Epoxides of naphthol aralkyl resins synthesized from epoxides of phenol resins, naphthols and para-xylene dichloride. These epoxy resins may be used singly or in combination of two or more. The blending amount of these may be a range which does not impair the purpose of the present invention, but is less than 50% by weight based on the total of StPNE and the difunctional 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, bisphenol, 4,4'-biphenol, and 2,2. Divalent phenols such as bisphenol, hydroquinone, resorcinol, catechol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetra (4 -Hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthol novolac, polyvinyl phenol, etc., represented by a trivalent or higher phenol, further a phenol, a naphthol, or a double Phenol A, bisphenol F, bisphenol S, bismuth bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, catechol, naphthalenediol, etc. Valence phenols and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylene glycol, p-xylene glycol dimethyl ether, diethylbenzene, diisopropenylbenzene, dimethoxy A polyvalent phenolic compound synthesized by a reaction of a crosslinking agent such as a methylbiphenyl group, a divinylbiphenyl group or a diisopropenylbiphenyl group. The softening point of the phenolic hardener is preferably in the range of 4 〇 to 150 ° C, more preferably 5 0 to 12 (TC. If it is lower than this, there is a problem of pressure sticking during storage, if higher than this, in the epoxy There is a problem in the kneading property and the formability at the time of preparation of the resin composition. Further, the melt viscosity at 150 ° C is preferably 1 kPa·s or less, and more preferably 〇.5 Pa · s or less. There is a problem in the kneading property and the formability in the preparation of the oxy-resin composition. -19- 201229122 The blending ratio of the epoxy resin and the hardener in the epoxy resin composition of the present invention is suitable for the functional group in the epoxy group and the hardener. The basis ratio is in the range of 0.8 to 1.5. In addition to this range, the unreacted epoxy group or the functional group in the curing agent remains after hardening, and the reliability, water absorption, and the like when the cured product is formed The inorganic cerium filling material used in the present invention is, for example, cerium oxide, aluminum oxide, chrome, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconium oxide, magnesium silicate. , talc, spinel, moldite, titanium oxide, etc., or a combination of these or more, or two or more types, It is preferable to use molten cerium oxide as a main component, and the form thereof may be, for example, a crushed shape or a spherical shape. Generally, a cerium oxide-based combination has a plurality of types of particle size distributions, and the average particle diameter range of the combined cerium oxide is used. It is preferably 0.5 to 100 μm. The content of the inorganic cerium filler is preferably in the range of 70 to 95% by weight, preferably 80 to 95% by weight, more preferably 8 5 to 95% by weight. If less than this, the organic component is contained. When the ratio is high, the durability is not sufficiently exhibited. On the other hand, if the ratio is larger than this, the thermal conductivity of the molded product is increased, and the decomposition rate of the organic component is increased, and the amount of the carbonized layer of the heat insulating layer is reduced. Further, in the epoxy resin composition of the present invention, if necessary, a polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, or the like may be appropriately blended. An oligomer or a polymer compound such as a coumarin resin or a phenoxy resin may be blended with an additive such as a pigment, a flame retardant, a shake imparting agent, a coupling agent, a fluidity enhancer, etc. The pigment is organic or inorganic. Body pigments, scaly pigments . Thixotropy imparting agents may be for example silicon oxide, such as polyethylene-based, castor oil-based, aliphatic acyl amine waxes, oxidized polyethylene waxes, organic bentonite

S -20- 201229122 Department, etc. Further, if necessary, a hardening accelerator such as an amine, an imidazole, an organic phosphorus or a Lewis acid may be blended. The blending amount is generally 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 blended with a release agent such as carnauba wax or OP wax, a coupling agent such as r-glycidoxypropyltrimethoxydecane, or carbon black. A coloring agent, a flame retardant such as antimony trioxide, a low stress agent such as eucalyptus oil, a slip agent such as calcium stearate, or the like. The curing agent of the present invention can be obtained by curing the above epoxy resin composition by a molding method such as casting, compression molding, or transfer molding. The temperature at which the hardened material is formed is generally 120 to 220 °C. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described based on Synthesis Examples, Examples and Comparative Examples. (Synthesis of a polyvalent hydroxy resin) Synthesis Example 1 A phenol novolak (a product of Showa Polymer, BRG-555, a hydroxyl equivalent of 105 g/eq, and a softening point 67) as a polyvalent hydroxy compound component was fed into a one-liter four-necked flask. °C, a melt viscosity of 0.08 Pa·s at 150 ° C, 105 g, 5.3 g of toluene, and 055 g (300 ppm) of p-toluenesulfonate as an acid catalyst, and the temperature was raised to 100 °C. Next, while stirring at 100 Torr, 73 g of styrene (〇.7 mol) was dropped over 3 hours to cause a reaction. Further to 1〇〇. (: After the reaction 2 -21 - 201229122 hours, 30% Na2CO3 0_049g was added for neutralization. Then, it was dissolved in MIBK 3 3 0g 'washed at 80 ° C for 5 times. Then, after distilling off MIBK under reduced pressure, The polyvalent hydroxy compound 170 g has a hydroxyl equivalent of 178 g/eq. 'The softening point is 78 ° C, and the melt viscosity at 150 ° C is 〇13 Pa · s. This resin is StPN - A. Synthesis Example 2 (Epoxy resin) Synthesis: 150 g of StPN-A obtained in Synthesis Example 1, 468 g of epichlorohydrin, and 70 g of diethylene glycol dimethyl ether were placed in a four-necked flask, and stirred and dissolved. After uniformly dissolved, a pressure of 130 mmHg was obtained. The solution was kept at 65 ° C, and 7 0.3 g of a 4 8 % aqueous sodium hydroxide solution was added dropwise over 4 hours. The water distilled off from the dropwise addition was separated from the epichlorohydrin in a separation tank, and the epichlorohydrin was returned to the reaction vessel. After the reaction is completed, the resulting salt is removed by filtration, and after further washing with water, epichlorohydrin is distilled off to obtain an epoxy resin of 185 g (StPNE - A). The epoxy equivalent is 246 g/eq., the softening point is 56 ° C, and the melt viscosity at 150 ° C is 0.1 MPa·s. Example 1~ 4. Comparative Examples 1 to 3 The epoxy resin (StPNE - A ) obtained in the above Synthesis Example 2, the epoxy resin, the curing agent, and the inorganic cerium material described below and the triphenyl benzene as a hardening accelerator were used. The epoxy resin composition was prepared by kneading with other additives at the blending ratios shown in Tables 1 to 2. The number in the table indicates the parts by weight in the blending.

S 201229122 For the difunctional crystalline epoxy resin, epoxy resin A: 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl epoxide (YX 4000H) Epoxy equivalent 195, melting point l〇5 ° C, melt viscosity at 150 ° C O.OllPa· s, manufactured by Mitsubishi Chemical), epoxy resin B: 3,3',5,5'-tetramethyl -4,4'-dihydroxybiphenylmethane epoxide (YSLV -8 0XY; epoxy equivalent 193, melting point 78 ° C, melt viscosity at 150 ° C 0.008 Pa _s, Nippon Steel Chemical Co., Ltd.) . Further, in terms of the epoxy resin to be compared, epoxy resin C: o-cresol novolac type epoxy resin (epoxy equivalent 200, softening point 65 ° C, manufactured by Nippon Steel Chemical Co., Ltd.). For the hardener component, a phenol aralkyl resin (PA; MEH-78 00SS (manufactured by Megumi Chemical Co., Ltd.), OH equivalent 175, softening point 67 〇C) or phenol novolac (PN; PSM-4261C Group Chemical Co., Ltd.) ), OH equivalent 103, softening point 82t). Using this epoxy resin composition, it was molded at 175 t, and further post-cured at 175 t for 12 hours to obtain a cured test piece, which was then supplied to various physical properties. The results are shown in Tables 3 to 4. 1) Measurement of epoxy equivalent weight Using a potentiometric titration apparatus, methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and the mixture was measured by using a potentiometric titration apparatus (0.1 mol/liter perchloric acid-acetic acid solution). 2) Softening point The automatic softening point device (Mingfeng Co., Ltd., Ltd., -23-201229122 ASP-M4SP) was used, and the JIS-K-2207 was used to measure by the ring method. 3) Melt viscosity Measured at 150 °C using a Brookfield-made CAP2000H rotary viscometer. 4) Adding an epoxy resin composition to a flat plate of a gelation tester (manufactured by Nisshin Scientific Co., Ltd.) heated to 175 ° C, and rotating it twice in 1 second using a fluororesin rod. The speed is stirred to investigate the gelation time required for the epoxy resin composition to harden. 5) Spiral flow-related spiral flow system The injection pressure of the epoxy resin composition (150 Kgf/cm2) and the hardening time of 3 minutes in the spiral flow measurement mold according to the specification (EMMI - 1-66) The conditions are shaped to investigate the flow length. 6) Linear expansion coefficient (CTE) and glass transition point (Tg) Tg, α 1 (CTE below Tg) was obtained by a thermomechanical measuring device of TMA120C type manufactured by Seiko Instruments at a temperature increase rate of I0 ° C/min. From the average 値 in the range of 30 to 50 ° C, α 2 (CTE above Tg) is obtained from the average 値 in the range of Tg + 20 ° C to 40 ° C. 7) Bending strength and bending elasticity -24-

S 201229122 According to JIS K 691 1, it is measured at room temperature by the 3-point bending test method. 8) Next, a molded product of 25 mm x 1.5 mm x 0.5 mm was formed between two sheets of copper plate by a compression molding machine at 175 ° C to evaluate the tensile shear strength after 18 hours of TC (after aging for 12 hours). 9) The water absorption rate is 25 ° C and the relative humidity is 50% as a standard state, with 85. 〇 The condition of relative humidity of 85% is the weight change rate after 100 hours of moisture absorption. 1 〇) Flame resistance A test piece having a thickness of W16 inch was formed and evaluated by the UL94V-Ο specification, and expressed by the total burning time of the five test pieces. [Table 1] Example 1 Example 2 Example 3 Example 4 S t PNE-A 41. 6 50.9 41. 5 50. 8 Epoxy resin A 41. 6 50. 9 Epoxy resin B 41. 5 50. 8 Epoxy resin CPA 66. 9 67. 1 PN 48. 2 48.4 Ceria 800 800 800 800 Hardening accelerator 1.2 1.2 1. 2 1.2 Carbon black 5 5 5 5 Carnauba wax 3 3 3 3 Ceria content (wt%) 83 83 83 83 -25- 201229122 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 S t PNE-A 87. 6 105. 7 41. 8 Epoxy Resin A Epoxy Resin B Epoxy Resin C 41. 8 PA 62. 4 66. 4 PN 44. 3 Ceria 800 800 800 Hardening accelerator 1. 2 1. 2 1. 2 Carbon black 5 5 . 5 Carnauba wax 3 3 3 Ceria content (wt%) 83 83 83 [Table 3] Example 1 Example 2 Example 3 Example 4 Gel time (seconds) 36 33 35 32. Spiral flow (cm) 87 80 92 86 Tg (t:) 120 125 132 135 CTE (<Tg, ΧΙΟ·5) 1. 0 1. 0 1. 0 1. 0 CTE (&gt;Tg, Xl〇-5) 4. 9 4. 8 5. 0 4. 9 Bending strength ( MP a) 121 125 118 120 Flexural modulus (GP a) 16. 1 17. 0 15. 5 16.0 Strength (MP a) 1. 28 1.23 1.29 1.26 Water absorption (w t %) 0. 21 0.22 0.21 0.22 Burning time (seconds) 68 79 65 73

S 201229122 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Gel time (seconds) 48 45 32 Helical flow (cm) 65 58 45 Ts (X:) 127 130 138 CTE (&lt;Tg, ΧΙΟ'5 ) 1. 1 1, 1 1.2 CTE OTg, xi〇'5) 5. 1 4. 8 4. 7 Strong bending strength (MPa) 137 141 148 Very flexible modulus (GP a) 17. 8 18. 1 21. 3 Next strength (MP a) 1.23 1. 22 1. 18 Water absorption (wt %) 0.22 0. 22 0.24 Burning time (seconds) 65 76 127 [Industrial use possibility] The epoxy resin composition of the present invention A cured product which is excellent in fluidity and hardenability and excellent in flame resistance, moisture resistance, and low elasticity can be suitably used for electrical and electronic parts packaging, circuit board materials, and the like. In particular, it is excellent in fluidity and flame resistance, and ensures excellent formability, and at the same time, the use of an environmentally-resistant flame retardant is not required or reduced. -27-

Claims (1)

201229122 VII. Patent application scope: 1. An epoxy resin composition which is contained in an epoxy resin composition containing an epoxy resin, a phenolic curing agent, and an inorganic cerium material, and the epoxy resin component is contained in the following The non-crystalline epoxy resin represented by the formula (1) and the difunctional crystalline epoxy resin having a melt viscosity at 150 ° C of 0.001 to 0.05 Pa · s have the following general formula with respect to the entire epoxy resin. (1) The content of the amorphous epoxy resin shown is 30% by weight or more, and the content of the difunctional crystalline epoxy resin is 30% by weight or more; (1) wherein 'G represents a glycidyl group, 1^ means a hydrogen or a hydrocarbon group having a carbon number of 1 to 6', and R2 represents a substituent represented by the following formula (a), and η represents the number of the first 20: Indicates the number of 0·1~2.5; [Chemical 2] HC-CH (a) r3 wherein 'R3' represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. 2. The epoxy resin composition as claimed in claim 1 wherein the two functional crystalline epoxy resin component is an epoxy resin represented by the following formula (2); -28 - S 201229122 OH OG (2) wherein R4 to Rh are selected from hydrogen and a hydrocarbon group having 1 to 6 carbon atoms, all of which may be the same or different; X represents a single bond, -0112-, -(:((:113)) 2-, -CO-, -0-, -S- or -S02-; G represents a glycidyl group 'm represents the number of 0 to 3. 3. The epoxy resin composition of the scope of the patent application, wherein The phenolic curing agent component is at least one selected from the group consisting of an aralkyl type phenol type curing agent and a novolac type phenol type curing agent. 4. The epoxy resin composition of the first aspect of the patent application, wherein the inorganic filler material The content of the epoxy resin composition is cured by the hardening of the epoxy resin composition according to any one of claims 1 to 4. -29- 201229122 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: No 201229122 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. S - 4-