JPH0912673A - Novel epoxy resin and its production, and epoxy resin composition and its cured item - Google Patents

Abstract

PURPOSE: To obtain a novel epoxy resin which gives an epoxy resin compsn. with a low viscosity and gives a cured item excellent in resistances to moisture and heat. CONSTITUTION: This epoxy resin is represented by the formula (wherein R is H or methyl; and (n) is 0-15).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides an epoxy resin composition excellent in low viscosity and a cured product excellent in moisture resistance and heat resistance. The present invention relates to a novel epoxy resin useful as a sealing material for parts and the like, a powder coating material, a laminated material, a composite material, a method for producing the same, an epoxy resin composition and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been industrially used in a wide variety of applications, but the required performance thereof has become more sophisticated in recent years. For example, there is a semiconductor encapsulating material in a typical field of a resin composition containing an epoxy resin as a main component, but in recent years, with an increase in the degree of integration of semiconductor elements, the package size has become larger and thinner, As for the mounting method, the transition to surface mounting is progressing, and the development of materials with more excellent solder heat resistance is desired.

Also, due to the recent trend of low cost and high integration, it has been replaced with a conventional dural inline package by transfer molding using a mold, such as a hybrid IC, a chip on board, a tape carrier package, a plastic pin grid array. There is an increasing number of methods of mounting bare chips by spot sealing using a liquid material without using a mold. However, liquid materials generally have the drawback of being less reliable than solid materials used for transfer molding. This is because the liquid material has a limit in viscosity, and the resin, curing agent,
This is because there are restrictions on the filler and the like.

In order to overcome these problems, it is desired to lower the viscosity of the epoxy resin, which is the main ingredient, in order to have excellent low hygroscopicity and to provide variations in curing agents, fillers and the like. It is rare. As low-viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol F
Type epoxy resins and the like are generally widely known, but these epoxy resins have problems in terms of moisture resistance and heat resistance.

[0005]

Accordingly, an object of the present invention is to provide an epoxy resin composition excellent in low viscosity and a novel epoxy resin which gives a cured product excellent in moisture resistance and heat resistance. To provide a manufacturing method. Another object of the present invention is to provide a novel epoxy resin composition which is excellent in low viscosity and gives a cured product excellent in moisture resistance and heat resistance. Further, another object of the present invention is to provide a cured product having excellent moisture resistance and heat resistance, which is obtained by curing such a novel epoxy resin composition.

[0006]

That is, the present invention provides a compound represented by the following general formula (1):

Embedded image (However, R represents a hydrogen atom or a methyl group, and n is 0 to 1
It is an epoxy resin represented by 5).

The present invention also provides the following general formula (2)

Embedded image (Wherein R represents a hydrogen atom or a methyl group) is a method for producing an epoxy resin of the above general formula (1), which comprises reacting bisphenol compound with epichlorohydrin in the presence of a metal hydroxide.

Furthermore, the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin represented by the general formula (1) is used as a part or all of the epoxy resin component. In addition, the present invention is a cured product obtained by curing such an epoxy resin composition.

The epoxy resin of the present invention represented by the above general formula (1) takes a liquid form to a solid form at room temperature depending on its molecular weight. In the general formula (1), the value of n representing the average number of repetitions is 0 to 15, and R is a hydrogen atom or a methyl group. If you focus on one molecule of epoxy resin, n
Is an integer, but the epoxy resin as a whole is usually put to practical use as a mixture having a molecular weight distribution. When the liquid epoxy resin is used by taking advantage of the low viscosity of the epoxy resin, the content of n = 0 is preferably 50% by weight or more, more preferably 80% by weight or more. The viscosity of the epoxy resin at this time is preferably 800 poises or less at 25 ° C., and more preferably 450 poises or less. Further, the epoxy resin of the present invention is preferably used as a sealing material for electronic parts, preferably of high purity, and the content of hydrolyzable chlorine is preferably 1,500 ppm or less.

The epoxy resin represented by the above general formula (1) of the present invention is synthesized by the epoxidation reaction of the bisphenol compound represented by the above general formula (2). The raw material of the epoxy resin used in the present invention The bisphenol compound used as is specifically 4,4 ′-(1,3-dimethylbutylidene) bisphenol or 4,4 ′-(1,3-
Dimethylbutylidene) bis (2-methylphenol), which is produced, for example, by reacting phenol or o-cresol with methyl isobutyl ketone. And
When synthesized according to this method, the obtained bisphenol compound usually contains 2,4 ′ in addition to 4,4′-substituted compound.
It is obtained as a mixture containing a -substituted product and a 2,2'-substituted product.

As the raw material of the epoxy resin used in the present invention, the higher the purity of the 4,4'-substituted product is, the more preferable. However, the raw material of the epoxy resin is 2,4'-substituted product or 2,4'-substituted product as long as the object of the present invention is not impaired. A mixture containing the 2'-substituted product can be used, but usually the purity of the 4,4'-substituted product is 80% by weight.
It is preferable to use the above bisphenol compound as a raw material, and more preferably, a 4,4′-substituted compound having a purity of 90% by weight or more is used. If the purity of the 4,4′-substituted product is lower than this, the reactivity and heat resistance of the epoxy resin are lowered.

The epoxy resin of the present invention is obtained by reacting the above bisphenol compound with epichlorohydrin in the presence of a metal hydroxide. Although the production method is not particularly limited, for example, after dissolving the bisphenol compound in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, at 50 to 150 ° C. , Preferably 6
A method of reacting at a temperature of 0 to 120 ° C. for 1 to 10 hours can be mentioned.

In the general formula (1), in order to suppress the production of the multimers in which n is 1 or more, it is necessary to use the epichlorohydrin in the reaction in excess of the phenolic hydroxyl group of the bisphenol compound. It is usually 1.5 mol or more, preferably 3 mol or more, relative to 1 mol of the phenolic hydroxyl group. If it is less than the above range, the amount of the epoxy resin multimer produced increases, the viscosity increases, and the epoxy equivalent increases and the heat resistance decreases.
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, per 1 mol of the hydroxyl group of the bisphenol compound.

After completion of the reaction, excess epichlorohydrin was distilled off, the residue was dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent was distilled off. , An epoxy resin can be obtained. If the content of multimers after synthesis is high,
The content of the monomer of n = 0 in the general formula (1) can be increased by a method such as molecular distillation.

As the curing agent used in the epoxy resin composition of the present invention, any of those generally known as curing agents for epoxy resins can be used, but the low viscosity of the epoxy resin of the present invention is utilized. When used as a liquid epoxy resin composition, it is preferable to use an acid anhydride curing agent. Specific examples of such an acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, dodecynylsuccinic anhydride, Nadic acid anhydride,
Examples include trimellitic anhydride.

Further, as other curing agents, for example,
Examples include dicyandiamide, polyhydric phenols, aromatic and aliphatic amines. Specifically, examples of the polyphenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol and the like. Divalent phenols or Tris- (4
-Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, trivalent or higher phenols represented by polyvinylphenol, and Phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone,
There are polyhydric phenolic compounds synthesized with a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol of divalent phenols such as resorcinol and naphthalenediol. , 4, 4 '
-Aromatic amines such as diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-xylylenediamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine And other aliphatic amines. In the epoxy resin composition of the present invention, only one kind of the curing agents exemplified above can be blended alone or as a mixture of two or more kinds.

The epoxy resin composition of the present invention also comprises
In addition to the epoxy resin of the present invention, there are 2 epoxy groups in the molecule.
You may use together the normal epoxy resin which has more than one piece. For example, bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol,
Divalent phenols such as 2,2′-biphenol, hydroquinone and resorcin, or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, Examples include glycidyl ether compounds derived from trivalent or higher phenols such as o-cresol novolac, or halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or as a mixture of two or more kinds, but the compounding amount of the epoxy resin of the present invention needs to be in the range of 5 to 100% by weight based on the whole epoxy resin. is there.

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 and phenoxy resin may be appropriately blended. Good.

The epoxy resin composition of the present invention also comprises
Additives such as an inorganic filler, a pigment, a retardant, a thixotropic agent, a coupling agent, and a fluidity improver can be added. Examples of the inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. , Organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicone type, castor oil type, aliphatic amide wax, oxidized polyethylene wax, organic bentonite type and the like.

Furthermore, if necessary, a conventionally known curing accelerator can be used in the resin composition of the present invention. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. As the addition amount,
Usually, it is in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

Further, if necessary, the resin composition of the present invention contains a release agent such as carnauba wax and OP wax, γ-
Coupling agents such as glycidoxypropyltrimethoxysilane, coloring agents such as carbon black, flame retardants such as antimony trioxide, low-stress agents such as silicone oil, and lubricants such as calcium stearate can be used.

The epoxy resin cured product of the present invention can be obtained by heating the above epoxy resin composition, which is excellent in low hygroscopicity, high solder heat resistance and the like. As a method for obtaining this cured product, casting, pouring, potting, dipping, drip coating, transfer molding, compression molding and the like are preferably used, and the temperature at that time is usually in the range of 100 to 220 ° C. .

[0023]

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples.

Example 1 (Synthesis Example of Epoxy Resin) 4,4'-Purity of 4,4'-body is 99.5% by Weight
(1,3-Dimethylbutylidene) bisphenol was used as a raw material. The purity of this product is measured using a column: 6 m
mφ × 150mm (Product name: Shim-pack CLC-ODS), mobile phase: acetonitrile / water = 60/40, flow rate: 1 ml
/ Min, temperature: 40 ° C. and detection: UV (254 nm).

200 g of the above 4,4 '-(1,3-dimethylbutylidene) bisphenol was added to epichlorohydrin 6
Dissolve in 85.2g and add 6 under reduced pressure (about 140mmHg)
4) 116.8 g of 48% sodium hydroxide aqueous solution at 5 ° C
It was dropped over time. During this time, the water produced was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropping was completed, the reaction was continued for another 30 minutes.

After the reaction was completed, the salt formed was removed by filtration, and the product was washed with water and then epichlorohydrin was distilled off to obtain 285 g of a colorless transparent liquid crude epoxy resin. Epoxy equivalent is 223, hydrolyzable chlorine is 5,000 p
pm. The measurement of hydrolyzable chlorine was according to the following method. That is, 0.5 g of resin sample is 100 ml
Weigh it into an Erlenmeyer flask with a stopper, and add 30 m of dioxane to it.
Add 1 to dissolve. Further, 5 ml of a 1N-KOH aqueous solution is added to this, and the mixture is boiled under reflux. Then, after cooling to room temperature, the reflux condenser is washed with 10 ml of methanol, and the whole amount is transferred to a 200 ml beaker. Further, the flask is washed with 100 ml of 80% acetone aqueous solution and transferred to a beaker.
Next, add 2 ml of concentrated nitric acid, and add 1/500 N-AgNO.
₃ Perform a potentiometric titration with an aqueous solution and perform a blank test.

The obtained epoxy resin was dissolved in 660 g of methyl isobutyl ketone, and 10% NaOH was added at 75 ° C.
An aqueous solution of 48.1 g was added and reacted for 2 hours. After the reaction was completed, the product was filtered, washed with water, and the methyl isobutyl ketone was distilled off to obtain 269.4 g of a single yellow liquid epoxy resin.
I got

The resulting epoxy resin had a hydrolyzable chlorine content of 320 ppm, an epoxy equivalent of 200, and E
The viscosity of the epoxy resin at 25 ° C. measured with a Brookfield viscometer was 343 poise. In addition, n in the resin
The purity of the diglycidyl ether of 4,4 ′-(1,3-dimethylbutylidene) bisphenol corresponding to = 0 is 9
It was 2.5% by weight, the content of the compound corresponding to the dimer with n = 1 was 6.0% by weight, and no multimer with n = 2 or more was detected. GPC for epoxy resin purity analysis
The measurement was performed. The measurement was performed using Tosoh Corp. HLC-82A as a device, and the column: Tosoh Corp. TS.
K-GEL2000 x 3 and TSK-GEL4000
× 1, solvent: THF, flow rate: 1 ml / min, temperature: 38
C. and detector: RI was used.

Further, the obtained epoxy resin was subjected to H-NMR measurement. Table 1 shows the results. In addition,
This H-NMR measurement is performed by JNM-G manufactured by JEOL Ltd.
X400 type, using heavy chloroform as a solvent,
It was performed at 400 MHz. In addition, the infrared absorption spectrum was measured. The results are shown in FIG.

[0030]

[Table 1]

Examples 2 and 3 Using the epoxy resin obtained in Example 1, the components were blended in the proportions shown in Table 2 and mixed uniformly to obtain a liquid epoxy resin composition. 12 using this epoxy resin composition
Heat curing was carried out at 0 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. About each of the obtained cured products, 25 ℃
Further, the volume resistivity at 150 ° C., the glass transition point, and the water absorption rate under the conditions of 133 ° C., 3 atmospheres, and 96 hours were measured. Table 2 shows the results.

Comparative Example 1 Using a bisphenol F type epoxy resin as an epoxy resin component, compounding, mixing and heat curing were carried out in the same manner as in Example 2 to obtain a cured product. Various physical properties of this cured product were measured in the same manner as in Examples 2 and 3 above. Table 2 shows the results.

[0033]

[Table 2]

[0034]

INDUSTRIAL APPLICABILITY The epoxy resin of the present invention is suitable for preparing a liquid epoxy resin composition having excellent low viscosity, and the epoxy resin composition prepared using this epoxy resin has a moisture resistance. And gives a cured product having excellent heat resistance. For this reason, the epoxy resin of the present invention and the epoxy resin composition using the same are suitable for use in electrical components such as semiconductor devices.
It is useful for applications such as sealing materials for electronic parts, powder coatings, laminated materials, and composite materials.

Claims (4)

[Claims] [Claim 1] The following general formula (1) (However, R represents a hydrogen atom or a methyl group, and n is 0 to 1
An epoxy resin represented by the number 5). 2. The following general formula (2): The method for producing an epoxy resin according to claim 1, wherein a bisphenol compound represented by the formula (wherein R represents a hydrogen atom or a methyl group) is reacted with epichlorohydrin in the presence of a metal hydroxide. 3. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 1 is used as part or all of the epoxy resin component. 4. A cured product obtained by curing the epoxy resin composition according to claim 3.