JP2006348064A - Epoxy resin, method for producing the same, epoxy resin composition using the same and its cured material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin or an epoxy resin composition capable of providing a cured material excellent in moisture resistance, heat resistance, adhesiveness, low dielectricity, weather resistance and transparency and useful for applications such as lamination, molding, casting and adhesion. <P>SOLUTION: The invention provides an epoxy resin having an adamantane structure represented by general formula (1) (wherein A is a 6-12C hydrocarbon group; R is a hydrogen atom or a methyl group; G is a glycidyl group; n is a number of 0-15), an epoxy resin composition obtained by formulating the epoxy resin and a curing agent as essential components, and its cured product. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy resin that gives a cured product excellent in moisture resistance, heat resistance, adhesion, low dielectric property, weather resistance, transparency and the like, a method for producing the epoxy resin, and an epoxy resin composition using the epoxy resin and its curing The present invention is suitably used for sealing electronic parts such as semiconductor elements and LED elements, circuit boards, coating materials, and composite materials.

  In recent years, with the advancement of the advanced material field in particular, development of a higher performance base resin has been demanded. For example, in the field of semiconductor encapsulation, the problem of package cracking has become serious due to the thinning and large area of packages corresponding to recent high-density mounting and the spread of surface mounting methods. As a base resin, improvement in moisture resistance, heat resistance, adhesion, impact resistance, etc. is strongly demanded. In the information communication field, a material having excellent low dielectric properties is desired in order to cope with an increase in the amount of information and an increase in communication speed.

  However, none of the conventionally known epoxy resins satisfy these requirements. For example, the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc. There is a problem in terms of moisture resistance. Moreover, as an improved heat resistance, an o-cresol novolac type epoxy resin is known, but there is a problem in moisture resistance and impact resistance.

JP 63-238122 A JP-A-64-79215 Japanese Patent Laid-Open No. 3-90075 JP 2003-171439 A

  Therefore, Patent Document 1 proposes an epoxy compound of a phenol aralkyl resin for the purpose of improving moisture resistance and impact resistance, but it is not sufficient in terms of heat resistance. Patent Document 2 proposes an aralkyl type epoxy compound of a dihydric phenol for the purpose of high heat resistance, but it is not sufficient in terms of moisture resistance and low dielectric properties. Furthermore, although a naphthol aralkyl type epoxy compound is proposed in Patent Document 3, it is still not sufficient in terms of low dielectric properties. Moreover, although the hydrogenated epoxy resin is disclosed by patent document 4 as what was excellent in a weather resistance and transparency, it is not enough at a heat resistant point.

  Accordingly, an object of the present invention is an epoxy resin and an epoxy resin composition which are excellent in moisture resistance, heat resistance, adhesiveness, low dielectric property, weather resistance and transparency, and are useful for applications such as lamination, molding, casting and adhesion. And providing a cured product thereof.

（但し、Ａは炭素数６〜１２の炭化水素基、Ｒは水素原子又はメチル基、Ｇはグリシジル基を示す。また、ｎは０〜１５の数を示す。） That is, the present invention is an epoxy resin having an adamantane structure represented by the following general formula (1).

(However, A represents a hydrocarbon group having 6 to 12 carbon atoms, R represents a hydrogen atom or a methyl group, G represents a glycidyl group, and n represents a number of 0 to 15)

（但し、Ａは炭素数６〜１２の炭化水素基を示し、Ｒは水素原子又はメチル基を示す。また、ｎは０〜１５の数を示す。） Moreover, this invention is a manufacturing method of the epoxy resin represented by General formula (1) characterized by making the polyhydric hydroxy resin represented by following General formula (2), and epichlorohydrin react.

(However, A shows a C6-C12 hydrocarbon group, R shows a hydrogen atom or a methyl group, and n shows the number of 0-15.)

  Furthermore, this invention is an epoxy resin composition which mix | blends the said epoxy resin as an essential component as an epoxy resin component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Furthermore, this invention is a hardened | cured material formed by hardening | curing the said epoxy resin composition.

  The epoxy resin of the present invention can be obtained by reacting a polyvalent hydroxy resin represented by the general formula (2) with epichlorohydrin, but in the invention of the epoxy resin, the production method is not limited thereto. However, by explaining the invention of the manufacturing method, it becomes easier to understand the epoxy resin of the present invention.

  In the polyvalent hydroxy resin represented by the general formula (2), A is a hydrocarbon group having 6 to 12 carbon atoms, and is preferably a cyclic group having an aromatic skeleton or an aliphatic skeleton. Examples of the aromatic skeleton include a benzene ring and a naphthalene ring, and examples of the aliphatic skeleton include a cyclohexane ring and a decalin ring. An aromatic skeleton is preferable from the viewpoint of heat resistance, and an aliphatic skeleton is preferable from the viewpoint of weather resistance and transparency. Examples of the aliphatic skeleton include cycloalkane and cycloolefin, and cycloalkane is preferable. When A is present at the terminal, it is a monovalent hydrocarbon group, and when A is present in the middle, it is a divalent hydrocarbon group. Moreover, although several A exists in 1 molecule, if it is a C6-C12 hydrocarbon group, they may be the same or different. Furthermore, when an aromatic skeleton or an aliphatic skeleton is referred to, an aromatic group or an aliphatic ring may be substituted with an alkyl group or the like within the above carbon number range.

  Such a polyvalent hydroxy resin can be usually obtained by reacting phenols with a specific crosslinking agent. Therefore, in the general formula (2), A can be referred to as a group derived from phenols or a nuclear hydride thereof. Preferred A is understood by explaining phenols.

  Specific examples of phenols include phenol, 2-methylphenol, 2,6-dimethylphenol, 1-naphthol, 2-naphthol, 1-hydroxy-5,6,7,8-tetrahydronaphthalene, 2-hydroxy- 5,6,7,8-tetrahydronaphthalene and the like. These phenols may be used alone or in combination of two or more.

ここで、Ｘは水酸基、塩素原子、臭素原子、ヨウ素原子が例示される。Ｒは水素原子又はメチル基を示すが、メチル基が好ましい。 As the crosslinking agent, an adamantane compound represented by the following general formula (3) is used.

Here, X is exemplified by a hydroxyl group, a chlorine atom, a bromine atom, and an iodine atom. R represents a hydrogen atom or a methyl group, preferably a methyl group.

  In the reaction between the phenol and the crosslinking agent, an excessive amount of phenol is used relative to the crosslinking agent. The amount of the crosslinking agent used is usually in the range of 0.1 to 0.9 mol, preferably in the range of 0.1 to 0.7 mol, per mol of phenols. If it exceeds the above range, the softening point of the resin becomes high, which hinders the molding workability. On the other hand, if the amount is less than this, the amount of excess phenols to be removed increases after the reaction, which is not industrially preferable. By adjusting this molar ratio, n in the general formula (2) varies. N represents an average number of repetitions, and is 1 to 15, preferably 1 to 8, and more preferably 1.1 to 3.

  This reaction is usually carried out at 50 to 200 ° C. for 1 to 20 hours, during which time the generated water or hydrogen halide is removed from the system. In some cases, an acid catalyst may be used, and the acid catalyst may be appropriately selected from known inorganic acids and organic acids. Examples of such an acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid, zinc chloride, aluminum chloride, iron chloride, Examples include Lewis acids such as boron trifluoride or solid acids such as activated clay, silica-alumina, and zeolite.

  Furthermore, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, and ethyl cellosolve, and aromatic solvents such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the reaction solvent.

  After completion of the reaction, in some cases, the catalyst is removed by a method such as neutralization or washing with water, and if necessary, the remaining solvent and unreacted phenols are removed from the system by a method such as distillation under reduced pressure. And If necessary, the obtained polyvalent hydroxy resin can be recrystallized using a solvent to obtain a bishydroxy compound in which n is 1 in the general formula (1). As the recrystallization solvent, alcohols such as methanol, ethanol, propanol and butanol, and aromatic solvents such as benzene, toluene, chlorobenzene and dichlorobenzene can be used. Furthermore, it is possible to obtain a polyvalent hydroxy resin having a cycloalkane ring or a cycloolefin ring by hydrogenating the polyvalent hydroxy resin obtained by the above reaction.

  The epoxy resin of this invention is represented by General formula (1). In the general formula (1), the same symbols as those in the general formula (2) are understood to mean the same thing. G represents a glycidyl group.

  The epoxy resin represented by the general formula (1) can be obtained by reacting the polyhydroxy resin represented by the general formula (2) with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction.

  For example, after dissolving the polyvalent hydroxy resin represented by the general formula (2) in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 50 to 150 ° C. Preferably, a method of reacting in the range of 60 to 120 ° C. for 1 to 10 hours can be mentioned. In this case, the amount of the alkali metal hydroxide used is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of the hydroxyl group in the polyvalent hydroxy resin. Epichlorohydrin is used in an excess amount relative to the hydroxyl group in the polyvalent hydroxy resin, but is usually 1.5 to 25 mol, preferably 2 to 1 mol of the hydroxyl group in the polyvalent hydroxy resin. The range is 15 moles. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. The target epoxy resin can be obtained. Although this epoxy resin has as a main component what is represented by General formula (1), naturally the thing which the epoxy group oligomerized as an ether bond is also contained. Furthermore, it can also be set as the epoxy resin which has a cycloalkane ring or a cycloolefin ring by hydrogenating the epoxy resin obtained by the said reaction.

  The epoxy resin of the present invention has excellent properties in heat resistance, moisture resistance and low dielectric constant due to the rigid adamantane structure with suppressed molecular motion having an alicyclic structure, and contains a curing agent. Thus, it can be suitably used as an epoxy resin composition for an electrical insulating material.

  The epoxy resin composition of this invention consists of an epoxy resin and a hardening | curing agent, and mix | blends the epoxy resin represented by General formula (1) as an essential component as an epoxy resin component.

  As the curing agent, any of those generally known as curing agents for epoxy resins can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines. Specific examples of these are as follows. In the resin composition of the present invention, one or more of these curing agents can be mixed and used.

  Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, There are phenols. Furthermore, dihydric phenols such as phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, Examples include polyhydric phenolic compounds synthesized by a condensing agent with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol and the like. Moreover, the polyvalent hydroxy resin represented by General formula (2) can also be used.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, and trimellitic anhydride.

  Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  Moreover, the epoxy resin composition of this invention can use all the normal epoxy resins which have 2 or more of epoxy groups in a molecule | numerator other than the epoxy resin of this invention. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , 1,2,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, trivalent or higher phenols such as o-cresol novolak, or halogenated bisphenols such as tetrabromobisphenol A There are sidyl ether compounds. These epoxy resins can be used alone or in combination of two or more. However, the use ratio of the epoxy resin of the present invention is 5 to 100%, preferably 50 to 100% in the whole epoxy resin.

  Further, in the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, phenoxy resin may be appropriately blended, You may mix | blend various additives, such as an inorganic filler, a pigment, a refractory agent, a thixotropic agent, a coupling agent, and a fluidity improver.

  Examples of inorganic fillers include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite. Also, release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, flame retardant aids such as antimony trioxide, and low levels such as silicone oil. You may mix | blend a lubricant, such as a stress agent and calcium stearate.

  Furthermore, a well-known hardening accelerator can be used as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. As addition amount, it is the range of 0.2-10 weight part normally with respect to 100 weight part of epoxy resins.

  The cured product of the present invention can be molded from the epoxy resin composition by a method such as casting, compression molding or transfer molding. The temperature at which the cured product is produced is usually in the range of 120 to 220 ° C.

  The resin composition or cured product of the present invention has properties excellent in heat resistance, moisture resistance and low dielectric properties, and is suitable for use as an electrical insulating material.

  The cured product obtained by curing the epoxy resin composition containing the epoxy resin of the present invention is excellent in moisture resistance, heat resistance, adhesiveness, low dielectric property, weather resistance, transparency, etc., semiconductor encapsulation, laminated board, It can be suitably used for applications such as coating materials and composite materials.

  Hereinafter, based on an Example and a comparative example, this invention is demonstrated concretely.

Reference Example 188 g of phenol and 26 g of water were charged in a 1000 ml four-necked flask, heated to 65 ° C. with stirring under a nitrogen stream, and 130 g of dimethyladamantane dibromide was added. Thereafter, the temperature was raised to 100 ° C. and the reaction was continued for 8 hours. After the reaction, hydrogen bromide and excess phenol produced by reprecipitation and washing with water were removed, followed by drying under reduced pressure at 180 ° C. to obtain 120 g of a polyvalent hydroxy resin mainly composed of a bisphenol compound. The melting point was 225 ° C.

Example 1
80 g of the polyvalent hydroxy resin obtained in the reference example was dissolved in 850 g of epichlorohydrin, and 40 g of 48% aqueous sodium hydroxide solution was added dropwise at 60 ° C. over 4 hours under reduced pressure (about 120 mmHg). During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of dropping, the reaction was continued for another hour. Thereafter, epichlorohydrin was distilled off and dissolved in 500 ml of methyl isobutyl ketone, and then the salt produced by filtration was removed. After washing with ion exchange water, methyl isobutyl ketone was distilled off to obtain 96 g of an epoxy resin. Epoxy equivalent was 265, melt viscosity at 150 ° C. based on ICI corn plate method was 0.032 Pa · s, and hydrolyzable chlorine was 550 ppm. Here, hydrolyzable chlorine was obtained by boiling 0.5 g of a resin sample in 30 ml of 1,4-dioxane and boiling and refluxing with 5 ml of 1N KOH / methanol solution for 30 minutes, and then using potentiometric titration with a silver nitrate solution. Determined by doing.

  A GPC chart of the obtained epoxy resin is shown in FIG. GPC measurement uses apparatus: HLC-82A (manufactured by Tosoh Corp.) and column: TSK-GEL 2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent: tetrahydrofuran, flow rate : 1.0 ml / min, temperature: 38 ° C., detector: RI. Moreover, after recrystallizing the obtained epoxy resin with isopropyl alcohol, the measurement of H-NMR and an infrared absorption spectrum was performed. The charts are shown in FIGS. 2 and 3, respectively.

Example 2 and Comparative Example 1
As the epoxy resin, the epoxy resin synthesized in Example 1 (epoxy resin A) and the bisphenol A type epoxy resin (epoxy resin B) were used, and methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika, MH-700) as a curing agent. Then, n-butyltriphenylphosphonium bromide was used as a curing accelerator, and the mixture shown in Table 1 was melt mixed at 80 ° C. with a mixing roll to obtain an epoxy resin composition. In addition, the numerical value in a table | surface shows the weight part in a mixing | blending. This epoxy resin composition was molded at 150 ° C., post-cured at 140 ° C. for 3 hours to obtain a cured product test piece, and then subjected to various physical property measurements.

  The glass transition point was calculated | required on the conditions of the temperature increase rate of 10 degree-C / min with the thermomechanical measuring apparatus. The water absorption was defined as the rate of change in weight when a specimen having a diameter of 50 mm and a thickness of 3 mm was used and moisture was absorbed for 24 hours at 121 ° C. and 2 atm after post-curing. The light transmittance was measured at 400 nm using a test piece having a thickness of 5 mm.

Epoxy resin GPC chart H-NMR chart of epoxy resin Infrared absorption spectrum of epoxy resin.

Claims (4)

The following general formula (1),

(Wherein A represents a hydrocarbon group having 6 to 12 carbon atoms, R represents a hydrogen atom or a methyl group, G represents a glycidyl group, and n represents a number of 0 to 15). Having epoxy resin. The following general formula (2),

Where A represents a hydrocarbon group having 6 to 12 carbon atoms, R represents a hydrogen atom or a methyl group, and n represents a number of 0 to 15. The method for producing an epoxy resin according to claim 1, wherein chlorohydrin is reacted.   In the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, the epoxy resin composition formed by mix | blending the epoxy resin of Claim 1 as an essential component.   Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 3.

Images