JP2981759B2 - Epoxy compound and epoxy resin composition - Google Patents

Description

The present invention relates to an epoxy compound which gives a cured product having high heat resistance and low hygroscopicity, and an epoxy resin composition obtained by blending the epoxy compound as an epoxy resin. About things.

(Prior Art) Epoxy resins are used as thermosetting resins in various fields such as lamination, painting, bonding, sealing and molding.

In recent years, as the required properties for polymer materials have become stricter, and the use conditions of electric and electronic devices using polymer materials have become severer, epoxy resins generally used at present cannot be sufficiently satisfied. .

For example, an epoxy resin composition using a phenol resin as a curing agent has been used for semiconductor encapsulation, but the required performance in this field has become even more severe. In other words, while the integration of the semiconductor device has been advanced and the size of the semiconductor element has been remarkably increased, the package itself has been reduced in size and thickness. In addition, the mounting of semiconductor elements has shifted to surface mounting. During surface mounting, since the semiconductor device is directly immersed in a solder bath and exposed to high temperatures, the moisture absorbed in the sealing material expands. Then, cracks are formed in the sealing material. For that purpose, a sealing material having good solder crack resistance is required to have high heat resistance and low moisture absorption, and sealing using a cresol novolak type epoxy resin which is currently mainly used and a phenol novolak resin as a curing agent. Materials have become less than satisfactory in both heat resistance and hygroscopicity.

In order to improve the disadvantages of the epoxy resin, there is an attempt to use a condensate of phenol and hydroxybenzaldehyde as an epoxy compound.In this case, heat resistance can be improved, but moisture absorption resistance cannot be improved, The solder crack resistance cannot be sufficiently improved. In addition, there is an attempt to improve the hygroscopicity by introducing an alkyl group into a curing agent or an epoxy compound, but in this case, heat resistance is deteriorated. As described above, it is difficult for the conventional epoxy resin composition to achieve both heat resistance and low moisture absorption.

(Problems of the Invention) The present invention provides an epoxy compound capable of providing a cured product having high heat resistance and low moisture absorption, and curing using the epoxy compound and having excellent heat resistance and moisture absorption resistance. It is an object of the present invention to provide an epoxy resin composition that gives a product.

(Means for Solving the Problems) As a result of various studies for solving the above problems, the present inventors have found that a polyvalent compound obtained by a condensation reaction of a phenol compound having a cyclic terpene skeleton with an aldehyde or a ketone. The epoxy compound obtained by the reaction between the phenol compound and epihalohydrin was able to achieve its purpose.

That is, the epoxy compound of the present invention was obtained by subjecting a phenol compound containing a cyclic terpene skeleton-containing polyhydric phenol compound obtained by adding a phenol to a cyclic terpene compound to a condensation reaction of an aldehyde or a ketone. It is a compound comprising a reaction product of a high molecular weight polyhydric phenol compound and epihalohydrin.

The epoxy resin composition of the present invention is a composition obtained by blending such an epoxy compound as an epoxy resin.

The high molecular weight polyhydric phenol compound as a raw material of the epoxy compound of the present invention is obtained by first adding a phenol to a cyclic terpene compound to obtain a cyclic terpene skeleton-containing polyhydric phenol compound, and containing the cyclic terpene skeleton-containing polyhydric phenol compound. The phenol compound is further subjected to a condensation reaction with aldehydes or ketones to increase the molecular weight.

The cyclic terpene compound as a raw material for producing the cyclic terpene skeleton-containing polyhydric phenol compound may be a monocyclic terpene compound or a bicyclic terpene compound, and specific examples thereof include: For example, the following are mentioned.

Limonene: Dipentin: an optical isomer of limonene.

Terpinolene: Pinen: Terpinene: Mentadien: Phenols which are the other raw materials for producing the cyclic terpene skeleton-containing polyhydric phenol compound include, for example, phenol, cresol, xylenol, propylphenol, nonylphenol, hydroquinone, resorcinol, methoxyphenol, bromophenol, bisphenol A , Bisphenol F and the like.

The addition reaction of the cyclic terpene compound with the phenol is carried out by adding 1 to 12 mol, preferably 2 to 8 mol, particularly preferably 2 to 8 mol of the phenol per 1 mol of the cyclic terpene compound.
1 to 1 at a temperature of 40 to 160 ° C in the presence of an acid catalyst.
Let it run for 0 hours. Hydrochloric acid, sulfuric acid,
Phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, activated clay and the like. The reaction solvent may not be used, but usually, a solvent such as an aromatic hydrocarbon, an alcohol, or an ether is used.

The cyclic terpene skeleton-containing polyhydric phenol compound thus produced is, for example, a compound produced from limonene and phenol, which is a compound represented by the following structural formula (I). The compound produced is a compound represented by the following structural formula (II).

Next, in order to produce the high-molecular-weight cyclic terpene skeleton-containing polyhydric phenol compound, an aldehyde or a ketone is subjected to a condensation reaction with the phenol compound containing the cyclic terpene skeleton-containing polyhydric phenol compound,
The phenol compound is preferably composed of only a cyclic terpene skeleton-containing polyhydric phenol compound, but may be a phenol compound (mixture) in which another phenol compound is used in combination with the cyclic terpene skeleton-containing polyhydric phenol compound. However, when used in combination, the proportion of the cyclic terpene skeleton-containing polyhydric phenol compound is at least 20% by weight, and preferably 40% by weight or more, based on the total amount with other phenol compounds. When the proportion of the cyclic terpene skeleton-containing polyhydric phenol compound is too small, a polymer having satisfactory physical properties cannot be obtained.

Aldehydes and ketones to be subjected to a condensation reaction with a phenol compound containing a cyclic terpene skeleton-containing polyhydric phenol compound include, for example, formaldehyde, acetaldehyde, benzaldehyde, paraformaldehyde,
Examples include hydroxybenzaldehyde, acetone, and cyclohexanone.

The reaction ratio of the phenol compound to the aldehydes and / or ketones in the condensation reaction is such that the aldehydes and / or ketones are 0.1 mol per mole of the phenol compound.
It is 1 to 1.0 mol, preferably 0.2 to 0.7 mol, and reacted at a temperature of 40 to 200 ° C. for 1 to 12 hours in the presence of an acidic catalyst. If the reaction ratio of the aldehydes and / or ketones is too high, the molecular weight will be remarkably increased and the heat resistance will be improved, but the handleability during molding will be poor due to the high viscosity. If the reaction ratio is too small, the effect of improving heat resistance is reduced.

As the acidic catalyst for the condensation reaction, for example, a normal acidic catalyst for producing a novolak resin such as a mineral acid such as hydrochloric acid and sulfuric acid, an organic acid such as oxalic acid and toluenesulfonic acid, and an organic acid salt exhibiting acidity are used. it can. The amount of the acidic catalyst used is 0.1 to 5 parts by weight based on 100 parts by weight of the phenol. In the condensation reaction, inert solvents such as aromatic hydrocarbons, alcohols and ethers can be used.

By reacting epihalohydrin with the high molecular weight polyhydric phenol compound obtained by the condensation reaction in this way, the epoxy compound of the present invention can be obtained. Representative examples of the reaction are described in detail below.

First, a high molecular weight polyhydric phenol compound is dissolved in epihalohydrin in an amount corresponding to 2 to 20 mol per mol of the phenolic hydroxyl group to form a uniform solution. Then, while stirring the solution, 1-2 moles of alkali metal hydroxide per 1 mole of phenolic hydroxyl group is added as a solid or aqueous solution and reacted. This reaction can be performed under normal pressure or reduced pressure, the reaction temperature is usually
The temperature is about 60 to 105 ° C. for the reaction under normal pressure, and about 50 to 80 ° C. for the reaction under reduced pressure. In the reaction, the reaction solution is azeotroped while maintaining a predetermined temperature as necessary, and the condensate obtained by cooling the volatilizing vapor is separated into oil and water, and the oil component from which water has been removed is returned to the reaction system. Dehydrate from the reaction system by the method. The alkali metal hydroxide is added intermittently or continuously in small amounts over 1 to 8 hours in order to suppress a rapid reaction. The total reaction time is usually from 1 to 10
About an hour.

After completion of the reaction, the insoluble by-product salt is separately removed or removed by washing with water, and then unreacted epichlorohydrin is removed by distillation under reduced pressure to obtain the desired epoxy compound.

As the epihalohydrin in this reaction, usually,
Epichlorohydrin or epibromohydrin is used, and as the alkali metal hydroxide, NaOH or KOH is usually used.

In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; benzyldimethylamine, 2,4,
Tertiary amines such as 6- (trisdimethylaminomethyl) phenol; 2-ethyl-4-methylimidazole;
Catalysts such as imidazoles such as -phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; and phosphines such as triphenylphosphine.

Further, in this reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; inactive polar solvents such as dimethyl sulfoxide and dimethylformamide; Organic solvents may be used.

Next, the epoxy resin composition of the present invention is a composition in which the epoxy compound of the present invention obtained as described above is contained as an epoxy resin, and other epoxy resins are contained in this epoxy compound. Can be used together.
Examples of other epoxy compounds that can be used in combination include bisphenol A, bisphenol F, resorcin, hydroquinone, methyl resorcin, phenol novolak, cresol novolak, resorcin novolak, bisphenol A novolak; various phenols and hydroxybenzaldehyde, crotonaldehyde, glyoxal, and the like. And epoxy resins produced from various phenols such as polyhydric phenols obtained by condensation reaction with various aldehydes and epihalohydrin.

The proportion of the epoxy compound of the present invention in the total epoxy resin in the epoxy resin composition of the present invention is preferably 20% by weight or more. If the proportion of the epoxy compound of the present invention is too small, the effect of the present invention (effect of providing a cured product having excellent heat resistance and moisture absorption resistance) cannot be sufficiently exhibited.

The epoxy resin composition of the present invention usually contains a curing agent, and further contains a curing accelerator, an inorganic filler, a coupling agent, a flame retardant, a plasticizer, an organic solvent, a reactive diluent, and a pigment. They can be appropriately blended.

As the curing agent, a commonly used curing agent for an epoxy resin is used, for example, a novolak phenol resin such as a novolak phenol resin or a novolac cresol resin; an acid anhydride such as tetrahydrophthalic anhydride or pyromellitic anhydride. Products; amines such as diaminodiphenylmethane and diaminodiphenylsulfone;

Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2,4,6-tris (dimethylaminomethyl)
Amines such as phenol and benzylmethylamine; and organic phosphorus compounds such as tributylphosphine and triphenylphosphine.

Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, and zircon. Examples of the flame retardant include brominated epoxy resin, antimony trioxide, and phosphoric acid.

The cured product of the epoxy resin composition of the present invention has higher heat resistance and less hygroscopicity than the cured product of the conventional epoxy resin composition. Therefore, the epoxy resin composition can be advantageously used in various fields such as sealing, lamination, molding, bonding, and painting.

(Examples and the like) Hereinafter, examples and comparative examples will be described in detail. Examples 1 to 3 are examples of the epoxy compound of the present invention, and Example 4
6 to 6 are examples of the epoxy resin composition of the present invention.

Example 1 3384 g (36 mol) of phenol and 34 g of boron trifluoride / diethyl ether complex were charged into a three-necked flask having a capacity of 5 equipped with a thermometer, a stirrer, and a condenser, and the limonene was heated at a temperature of 70 to 80 ° C. 816 g (6 mol) was added dropwise over 3 hours,
The mixture was further stirred at the same temperature for 2 hours. Next, the product was washed three times with distilled water 1, and then phenol and by-products were distilled off under reduced pressure. Finally, the product was kept at 160 ° C. and 5 mmHg for 1 hour to obtain 1520 g of a cyclic terpene skeleton-containing polysaccharide. A trivalent phenol compound was obtained. The purity of this polyhydric phenol compound was 89% as a result of liquid chromatography analysis.

Next, into a three-necked flask having an internal volume of 3 equipped with a thermometer, a stirrer, and a cooling tube, 1100 g of the cyclic terpene skeleton-containing polyhydric phenol compound produced as described above, 1,000 g of toluene, and 5 g of oxalic acid were charged. The temperature was raised to 80 ° C to dissolve uniformly. Next, while maintaining the inside of the flask at 80 ° C., 75 g of a 36% aqueous formaldehyde solution was added dropwise over 1 hour, and after the completion of the addition, the reaction was further carried out at 80 ° C. for 1 hour.
Then, the temperature was raised to remove water and toluene, and finally
Water and toluene were completely removed by holding at 160 ° C. under a reduced pressure of 5 mmHg for 1 hour. The resulting polymerized polyhydric phenol compound was a yellow solid having a softening point of 126 ° C.

Further, 1020 g of the polymerized polyhydric phenol compound produced as described above and epichlorohydrin 277 were placed in a flask having an internal volume of 3 provided with a thermometer, a stirrer, and a condenser.
5 g and 1080 g of isopropyl alcohol were charged, and the mixed solution was heated to 35 ° C., and 544 g of a 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour.
During this time, the temperature was gradually raised so that the temperature in the system reached 65 ° C. at the end of the dropping. Thereafter, the reaction was carried out at 65 ° C. for 30 minutes. After the completion of the reaction, the product was washed with water to remove by-product salts and excess sodium hydroxide. Next, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy compound.

This crude epoxy compound was dissolved in 1300 g of toluene, 30.0 g of a 48.5% by weight aqueous sodium hydroxide solution was added, and reacted at a temperature of 65 ° C. for 1 hour. After the completion of the reaction, sodium phosphate monobasic was added to neutralize the excess sodium hydroxide, and washed with water to remove by-product salts. Next, the solvent was completely removed under reduced pressure to obtain an epoxy compound. This epoxy compound has an epoxy equivalent of 249 g / eq. And a softening point of 68.
° C. as a pale yellow solid.

Example 2 In place of 75 g of the 36% aqueous solution of formaldehyde used in Example 1, 80 g of benzaldehyde was used, and the amount of the polymerized polyhydric phenol compound used in the reaction with epihalohydrin was changed to 1050 g. The reaction was carried out in accordance with No. 1 and post-treatment was performed to obtain an epoxy equivalent of 252 g / eq. And a softening point.
An epoxy compound at 71 ° C. was obtained.

Example 3 Using 816 g (6 mol) of terpinene instead of limonene,
Otherwise, the reaction was carried out in the same manner as in Example 1 and post-treatment was carried out to obtain 1480 g of a cyclic terpene skeleton-containing polyhydric phenol compound. According to the result of liquid chromatography analysis, the polyhydric phenol compound had a purity of 86%.

Next, using this polyhydric phenol compound,
Novolak reaction is carried out in the same manner as in
1,50 g of a polymerized polyphenol compound as a yellow solid at 1 ° C
I got

Next, 1020 g of this polymerized polyhydric phenol compound and 2775 g of epichlorohydrin were reacted in the same manner as in Example 1 and post-treated to obtain a light yellow solid epoxy having an epoxy equivalent of 254 g / eq. And a softening point of 70 ° C. 1250 g of compound was obtained.

Examples 4-6 Comparative Examples 1-2 As shown in Table 1, Example 1 was used as an epoxy compound.
Each of the epoxy compounds, ortho-cresol novolak type epoxy compounds obtained in the above-mentioned steps 3 or 3, or an epoxy compound derived from phenol and hydroxybenzaldehyde is used, a phenol novolak resin is used as a curing agent, and a brominated epoxy compound and a trioxide are used as a flame retardant. Using antimony, using triphenylphosphine as a curing accelerator, using silica powder as a filler, using epoxysilane as a surface treatment agent, and using carnauba wax as a release agent, compounding each epoxy resin composition did.

Next, each formulation was mixed for 90 to 11 using a mixing roll.
Each melt mixture obtained by melt-mixing at a temperature of 0 ° C. for 5 minutes was taken out in the form of a sheet and pulverized to obtain each molding material. Using each of these molding materials, a low pressure transfer molding machine was used to mold at a mold temperature of 180 ° C and a molding time of 180 seconds. The test piece for measuring the moisture absorption and the 44-pin FPP (flat plastic package) in which the simulated element was sealed Was post-cured at 180 ° C. for 8 hours. The results of testing the glass transition temperature, moisture absorption rate, and solder heat resistance after the post-curing are as shown in Table 1. The molding materials of Examples 4 to 6 were compared with the molding materials of Comparative Examples 1 and 2. An excellent cured product having a high glass transition temperature and a low moisture absorption was provided, and was suitable for semiconductor encapsulation.

Notes on Table 1: * 1: Yuka Ciel Epoxy Co., Ltd. Epicoat 180H65, epoxy equivalent 201, softening point 67 ° C * 2 ... Yuka Ciel Epoxy Co., Ltd. Epicoat 1032H60, epoxy equivalent 169, softening point 62 * 3: Yuka Ciel Epoxy Co., Ltd. Epicoat 5050, epoxy equivalent 385, bromine content 49% * 4: Gunei Chemical Co., Ltd., softening point 85 ° C * 5: Tatsumori company name RD- 8 * 6: Shin-Etsu Chemical Co., Ltd. KBM-403 * 7: Calculated from the transition point of the thermal expansion curve using TMA.

* 8: Moisture absorption after 200 hours at 121 ° C, 100% RH * 9: Sixteen 44-pin FPPs were absorbed at 85 ° C, 85% RH for 168 hours, then immersed in a 260 ° C solder bath for 10 seconds to prevent cracking. The number of occurrences was determined.

(Effect of the Invention) The epoxy compound of the present invention has high heat resistance and can give a cured product having low hygroscopicity. The epoxy resin composition of the present invention using this epoxy compound can be used for sealing, lamination, molding,
It can be used advantageously in the fields of bonding and painting.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-69255 (JP, A) JP-A-55-89318 (JP, A) JP-A-55-94921 (JP, A) JP-A-4- 26642 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/08 C08G 59/20-59/38 C08L 63/00-63/10 C07D 303/24-303/27

Claims (3)

(57) [Claims] An aldehyde or ketone is subjected to a condensation reaction with a phenol compound containing a cyclic terpene skeleton-containing polyhydric phenol compound obtained by adding a phenol to a cyclic terpene compound. An epoxy compound comprising a reaction product of a polyhydric phenol compound and epihalohydrin. 2. The epoxy compound according to claim 1, wherein the cyclic terpene skeleton-containing polyhydric phenol compound is obtained by adding 1 mol of the cyclic terpene compound and 2 mol of phenols. 3. An epoxy resin composition comprising the epoxy compound according to claim 1 or 2 as an epoxy resin.