JPH07330645A - Compound of polyphenols, epoxy resin, epoxy resin composition and cured material thereof - Google Patents

Abstract

PURPOSE:To obtain a new compound useful for a sealing material of electric and electronic parts, a laminating material, etc., providing a cured material having excellent heat resistance and water resistance. CONSTITUTION:A compound of formula I (R and Q are H, a halogen, a 1-8C alkyl or an aryl) such as a compound of formula II. The compound of formula I is obtained by condensing a compound of formula III with a phenol in the presence of an acid catalyst. p-Toluenesulfonic acid, sulfuric acid and hydrochloric acid are preferable as the acid. The amount of the catalyst used is preferably 0.001-0.1mol based on 1mol of the compound of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenol compound, an epoxy resin, an epoxy resin composition containing them, which gives a cured product excellent in heat resistance and water resistance, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, in the field of electric and electronic parts, especially IC sealants, cresol novolac type epoxy resin,
As the curing agent, an epoxy resin composition containing a phenol novolac resin and a curing accelerator as main components is widely used. However, the high density and high integration of ICs in recent years have made it necessary for sealing agents to have high heat resistance and low water absorption. In particular, the harsh condition of solder immersion in high-density mounting of ICs further increases the requirements for high heat resistance and low water absorption of cured products.

[0003]

However, the conventional epoxy resin has a drawback that as the molecular weight increases, the toughness of a cured product obtained by using the epoxy resin increases, but the heat resistance decreases. Further, although a cured product obtained by mixing a polyfunctional epoxy resin such as cresol novolac epoxy resin in order to compensate for the decrease in heat resistance has high heat resistance, it has a drawback that toughness decreases and water absorption increases. . Further, in the conventional resin composition,
A phenol novolac resin has been generally used as a curing agent for an epoxy resin, but a cured product using this is still in an insufficient stage in terms of heat resistance and water resistance. On the other hand, with the recent remarkable development of the electronic industry and the like, the heat resistance and water resistance required for the electric insulating materials used for these have become more and more severe, and the emergence of a curing agent excellent in these properties has been awaited. Has been.

[0004]

In view of these circumstances, the inventors of the present invention have earnestly studied for an epoxy resin and a curing agent which give a cured product having excellent heat resistance and water resistance, and as a result, have completed the present invention. Arrived

That is, the present invention is based on the equation (1)

[Chemical 2]

(In the formula, R and Q each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each P and Q may be the same or different from each other. (2) a polyphenol compound represented by the formula (2), an epoxy resin obtained by glycidyl etherification of the phenolic hydroxyl group of the polyphenol compound of the formula (1) described in (1) above, (3) (a) an epoxy resin ( b) an epoxy resin composition containing the polyphenol compound of formula (1) described in (1) above,

(4) (a) Epoxy resin composition described in (2) above (b) Epoxy resin composition containing a curing agent, (5) (a) Epoxy resin composition described in (2) above, (b) above (1) An epoxy resin composition containing the polyphenol compound of the formula (1) described in 1.

(6) The above (3) containing a curing accelerator,
(4) or (5) described epoxy resin composition, (7) a cured product obtained by curing the above (3), (4), (5) or (6) epoxy resin composition Is.

The compound represented by the formula (1) is represented by, for example, the formula (2)

[0010]

[Chemical 3]

It can be obtained by subjecting a compound represented by the formula (wherein Q has the same meaning as in formula (1)) and a phenol to a condensation reaction in the presence of an acid catalyst.

The compound represented by the formula (2) is disclosed in JP-A-55-
7235, JP-A-63-14749, JP-A-2-2
In addition to the method described in JP-A No. 33622 and JP-A No. 4-99744, any known method can be used.

Here, the phenols refer to compounds having at least one phenolic hydroxyl group, and examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methyl. Various o-, m-, p- isomers of alkylphenol represented by butylphenol, di-t-butylphenol, etc., or vinylphenol,
Various o-m-p-isomers of allylphenol, propenylphenol, ethynylphenol, or cycloalkylphenol typified by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, or substituted phenols such as phenylphenol, or α-naphthol. , Β-naphthol and other naphthols. These phenols are 1
Only one kind may be used, or two or more kinds may be used in combination.

When carrying out the condensation reaction, the amount of phenols used is preferably in the range of 4 to 40 mol, particularly preferably 5 to 30 mol, per 1 mol of the compound represented by the formula (2).

In the above condensation reaction, it is preferable to use an acid catalyst, and various kinds of acid catalysts can be used, but inorganic or organic acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and oxalic acid, and boron trifluoride. Lewis acids such as anhydrous aluminum chloride and zinc chloride are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable. The amount of these acid catalysts used is not particularly limited, but is 0.001 to the amount of the compound represented by the formula (2).
It can be used in a 0.1-fold molar range.

The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the case of using an organic solvent include toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is preferably 50 to 300% by weight, and particularly preferably 100 to 250% by weight, based on the total weight of the raw materials charged.

The reaction temperature is preferably 50 to 180 ° C, particularly preferably 70 to 170 ° C. Reaction time is usually 2 to 30
Time, preferably 3 to 25 hours. It is preferable to remove the water generated during the reaction to the outside of the reaction mixture by using a fractionating tube or the like in order to carry out the reaction quickly.

After completion of the reaction, neutralization or washing is carried out to adjust the pH value to 3-7, preferably 5-7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylenetriamine and trihydrate. Various basic substances such as organic amines such as ethylene tetramine, aniline and phenylenediamine may be used as the neutralizing agent for treatment. In the case of washing with water, it may be carried out according to a conventional method. For example, water in which the above-mentioned neutralizing agent is dissolved is added to the reaction generation system, and the liquid separation and extraction operation is repeated.

After the neutralization treatment, unreacted phenols and solvent are distilled off under reduced pressure heating to concentrate the product,
The polyphenol compound of the present invention represented by the formula (1) can be obtained.

The epoxy resin of the present invention can be obtained by reacting the compound represented by the formula (1) thus obtained with epihalohydrin in the presence of an alkali metal hydroxide. As such a reaction method,
A known method can be adopted.

For example, the obtained compound represented by the formula (1) (hereinafter, the compound represented by the formula (1) is referred to as a polyphenol compound unless otherwise specified) and excess epichlorohydrin, epibromhydrin, epiiodo. To obtain an epoxy resin of the present invention by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a dissolved mixture of epihalohydrin such as hydrin, or by reacting at a temperature of 20 to 120 ° C. while adding. Can be done. Most preferably, epichlorohydrin is used above.

In the reaction for obtaining the epoxy resin of the present invention, an aqueous solution of the alkali metal hydroxide may be used, in which case an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system. A method may be used in which water and epihalohydrin are continuously flowed out under reduced pressure or normal pressure, and further liquid separation is performed to remove water and epihalohydrin is continuously returned to the reaction mixture.

Further, it can be obtained by adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst to a dissolved mixture of a polyphenol compound and epihalohydrin and reacting at 50 to 150 ° C. Alternatively, a solid or aqueous solution of an alkali metal hydroxide may be added to the halohydrin etherified product of a polyphenol compound, and the mixture may be reacted again at a temperature of 20 to 120 ° C. for dehydrohalogenation (ring closure).

Usually, the amount of epihalohydrin used in these reactions depends on the hydroxyl group of the polyphenol compound.
It is usually 1 to 20 mol, preferably 2 to 10 mol, based on the equivalent amount. The amount of the alkali metal hydroxide used is 0.8 to 15 mol, preferably 0.9 to 11 mol, based on 1 equivalent of the hydroxyl group of the polyphenol compound. Further, in order to allow the reaction to proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide in addition to alcohols such as methanol and ethanol.

When alcohols are used, the amount thereof used is 2 to 20% by weight, more preferably 4 to 15% by weight, based on the amount of epihalohydrin. When an aprotic polar solvent is used, it is 5 to 1 relative to the amount of epihalohydrin.
The amount is 00% by weight, more preferably 10 to 90% by weight.

After washing these reaction products of the epoxidation reaction with or without washing with water, heating under reduced pressure at 150 to 250 ° C.
Excessive epihalohydrin and other added solvents are removed at a pressure of 10 mmHg or less. Further, in order to obtain an epoxy resin having a smaller amount of hydrolyzable halogen, the recovered epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. Can be added to carry out further reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, and particularly preferably 0.05 to 0.1 mol, per 1 equivalent of the hydroxyl group of the polyphenol compound used for the epoxidation.
2 mol. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After the completion of the reaction, the formed salt is removed by filtration, washing with water and the like, and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

The epoxy resin composition of the present invention can be obtained by using the epoxy resin of the present invention and / or the polyphenol compound of the present invention as an essential component, and further adding a curing accelerator and the like if necessary. (3),
In the epoxy resin composition of the present invention described in (5) and (6), the polyphenol compound of the present invention can be used as the component (b) alone or in combination with other curing agents. When used in combination, the proportion of the polyphenol compound of the present invention in the total curing agent is preferably 30% by weight or more, and particularly preferably 40% by weight or more. As the curing agent that can be used in combination with the polyphenol compound of the present invention, an amine compound such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a dimer of linolenic acid and ethylenediamine are synthesized. Polyamide resin, phthalic anhydride, trimellitic anhydride,
Acid anhydride compounds such as pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, cresol novolac And other novolak resins and modified products thereof, imidazole, BF ₃ -amine complex, guanidine derivative and the like. These curing agents may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention described in (4), (5) and (6) above, the epoxy resin of the present invention is used alone as the component (a) or in combination with other epoxy resins. can do. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, and particularly preferably 40% by weight or more.
When used in this case, the epoxy resin used is usually a compound having two or more epoxy groups in one molecule, and is not particularly limited as long as it is a compound generally used for electronic devices. For example, novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, Epoxy resins obtained from aromatic dihydric phenols such as bisphenol I type epoxy resins and biphenyl type epoxy resins, glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epihalohydrin, and diamino Examples thereof include glycidylamine type epoxy resins obtained by reacting a polyamine such as diphenylmethane or isocyanuric acid with epihalohydrin. These epoxy resins may be used alone or 2
You may mix 1 or more types. The epoxy resin used is not limited to the above.

In the epoxy resin composition described in (3) and (6), examples of the epoxy resin as the component (a) include the epoxy resins of the present invention and the other epoxy resins described above. Further, in the epoxy resin compositions described in (4) and (6), examples of the curing agent as the component (b) include the above-mentioned curing agents in addition to the polyphenol compound of the present invention.

In the epoxy resin composition of the present invention,
The amount of the curing agent as the component (b) used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of the epoxy resin as the component (a). If the amount is less than 0.7 equivalent or more than 1.2 equivalent to 1 equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

A curing accelerator may be used in combination in the epoxy resin composition of the present invention. Examples of usable curing accelerators are imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4,0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. When the curing accelerator is used, the amount used is 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin (component (a)) and the curing agent (component (b)), fillers and other additives are used, if necessary, until uniform using an extruder, a kneader, a roll or the like. Mix thoroughly to obtain a resin composition,
After the resin composition is melted, it is molded using a casting or transfer molding machine, and further, at 80 to 200 ° C. for 2 to
A cured product can be obtained by heating for 10 hours.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like to prepare glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnating the base material with heat and drying can also be hot-press molded to obtain a cured product. The amount of the diluent solvent used in this case is usually 10 to 7 relative to the total weight of the epoxy resin composition of the present invention and the diluent solvent.
It is 0% by weight, preferably 15 to 65% by weight.

Since the cured product thus obtained has excellent heat resistance and water resistance, it can be used in a wide range of fields where heat resistance and water resistance are required. Specifically, the sealing material,
It is useful as all electrical and electronic materials such as laminated plates and insulating materials. It can also be used in fields such as molding materials, adhesives, composite materials, paints and resists.

[0036]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. In the following, parts are parts by weight unless otherwise specified. Further, the glass transition point, water absorption rate, and bending strength in Examples and Comparative Examples were measured under the following conditions. Glass transition temperature thermomechanical measuring device (TMA): TM- manufactured by Vacuum Riko Co., Ltd.
7000 Temperature rising rate: 2 ° C./min. Water absorption test piece (cured product): diameter 50 mm, thickness 3 mm, disk, weight increase rate (%) after boiling in 100 ° C. water for 24 hours Bending strength Conforms to JIS K-6911

Example 1 A flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer was charged with phenol 940 while purging with nitrogen gas.
Part, the following formula (3)

[0038]

[Chemical 4]

105 parts of the compound represented by and 1.2 parts of p-toluenesulfonic acid (monohydrate) were charged, and the mixture was stirred at 1
The temperature was raised to 40 ° C. The reaction was stirred for an additional 10 hours. Then, 2.5 parts of a 20% by weight sodium dihydrogen phosphate aqueous solution was added, and after stirring, the excess phenol was removed under reduced pressure by heating to obtain the following formula (4).

[0040]

[Chemical 5]

270 parts of the polyphenol compound of the present invention represented by the following (the following compound (A)) was obtained. The resulting compound (A) has a softening point of 114.2 ° C. and a hydroxyl equivalent of 138.
It was g / eq.

Example 2 The reaction was carried out in the same manner as in Example 1 except that m-cresol portion was used instead of phenol, and the following formula (5) was used.

[0043]

[Chemical 6]

301 parts of the polyphenol compound of the present invention represented by the following (the following compound (B)) was obtained. The resulting compound (B) has a softening point of 121.3 ° C. and a hydroxyl equivalent of 152.
It was g / eq.

Examples 3 to 4 and Comparative Example 1 An o-cresol novolac type epoxy resin (EOCN1020, manufactured by Nippon Kayaku Co., Ltd., softening point 6) as an epoxy resin.
5.1 ° C., epoxy equivalent 200 g / eq), compounds (A) to (B) obtained as a curing agent, phenol novolac resin as a comparison (softening point 80.2 ° C., hydroxyl equivalent 10
6 g / eq), triphenylphosphine (TPP) was used as a curing accelerator, and compounded in the composition shown in Table 1 to give 70
Knead by roll for 15 minutes at 150 ℃, molding pressure 50k
Transfer molding was performed at g / cm ² for 180 seconds, and thereafter, the test piece was prepared by curing at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours, and the glass transition point and water absorption were measured. The results are shown in Table 1. Further, in the table, the numerical value in the column of composition of formulation shows parts by weight.

[0046]

Table 1 Table 1 Example 1 Example 2 Comparative Example 1 Composition of formulation EOCN1020 100 100 100 Compound (A) 72.5 Compound (B) 76.0 Phenol novolac resin 53.0 TPP 1 1 1 Physical properties of cured product Glass transition point (° C. ) 185 188 153 Water absorption rate (%) 0.96 0.87 1.30 Bending strength (kg / mm ² ) 11.3 11.0 9.3

Example 5 The compound (A) obtained in Example 1 was subjected to nitrogen gas purging in a flask equipped with a thermometer, a condenser and a stirrer.
138 parts, 370 parts of epichlorohydrin, and 92.5 parts of dimethyl sulfoxide were charged and dissolved. Flake-shaped sodium hydroxide (99% pure) heated to 50 ° C 4
0.4 parts were added in portions over 90 minutes, and then 60 ° C
For 2 hours and at 70 ° C. for 1 hour. After completion of reaction, 1
Dimethyl sulfoxide and epichlorohydrin were distilled off under heating and reduced pressure at 30 ° C., and 390 parts of methyl isobutyl ketone was added to the residue and dissolved.

Further, this methyl isobutyl ketone solution was heated to 70 ° C. to prepare a 30% by weight sodium hydroxide aqueous solution 1
After adding 3.3 parts and reacting for 1 hour, washing with water was repeated 3 times to make the pH neutral. Further, the water layer is separated and removed, and methyl isobutyl ketone is distilled off from the oil layer under heating and reduced pressure by using a rotary evaporator to obtain the following formula (6).

[0049]

[Chemical 7]

188 parts of the epoxy resin (EA) of the present invention represented by the formula (G represents a glycidyl group) were obtained. The obtained epoxy resin had a softening point of 85.2 ° C. and an epoxy equivalent of 214 g / eq.

Example 6 The reaction was carried out in the same manner as in Example 1 except that 1220 parts of 2,6-xylenol was used instead of phenol, and the following formula (7) was used.

[0052]

[Chemical 8]

304 parts of the polyphenol compound of the present invention represented by Then, an epoxidation reaction was carried out in the same manner as in Example 5 except that the obtained compound (166) represented by the formula (7) was used.

[0054]

[Chemical 9]

202 parts of the epoxy resin (EB) of the present invention represented by the formula (G represents a glycidyl group) were obtained. The obtained epoxy resin had a softening point of 93.4 ° C. and an epoxy equivalent of 234 g / eq.

Examples 7 to 8 and Comparative Example 2 Obtained epoxy resins (EA) to (EB), for comparison, o-cresol novolac type epoxy resin (EOCN1)
020, manufactured by Nippon Kayaku Co., Ltd., softening point 65.1 ° C., epoxy equivalent 200 g / eq, phenol novolac as a curing agent (hydroxyl group equivalent 106 g / eq, softening point 80.2).
℃), triphenylphosphine (TP
P) and compounded in the composition shown in Table 2 at 70 ° C.
Kneading with minute rolls, 150 ℃, molding pressure 50kg / cm
Transfer molding at 180 for ² seconds, then 160
A glass transition point, a water absorption rate, and a bending strength were measured by curing the test piece at 2 ° C. for 2 hours and then at 180 ° C. for 8 hours to prepare a test piece. The results are shown in Table 2. In the table, the numerical value in the column of composition of formulation shows parts by weight.

[0057]

Table 2 Example 7 Example 8 Comparative Example 2 Composition of the formulation Epoxy resin (EA) 100 Epoxy resin (EB) 100 EOCN1020 100 (Epoxy equivalent (g / eq)) 214 234 200 Phenol novolac 49.5 45.3 53.0 TPP 1 1 1 1 Physical properties of cured product Glass transition point (℃) 183 189 154 Water absorption rate (%) 0.92 0.88 1.28 Bending strength (Kg / mm ² ) 12.6 13.1 9.1

Examples 9 to 10 Epoxy resins (EA) to (EB), compounds (A) to (B) as a curing agent, and triphenylphosphine (TPP) as a curing accelerator were used. And then 7
Knead with a roll for 15 minutes at 0 ℃, 150 ℃, molding pressure 50
Transfer molding was performed at 180 kg / cm ² for 180 seconds, and thereafter, curing was performed at 160 ° C. for 2 hours and then at 180 ° C. for 8 hours to prepare a test piece, and the glass transition point, water absorption, and bending strength were measured. The results are shown in Table 3. In the table, the numerical value in the column of composition of formulation shows parts by weight.

[0059]

Table 3 Table 9 Example 9 Example 10 Composition of formulation Epoxy resin (EA) 100 Epoxy resin (EB) 100 Compound (A) 64.5 Compound (B) 65.0 TPP 1 1 Physical properties of cured product Glass transition point (° C. ) 192 196 Water absorption (%) 0.96 0.92 Bending strength (Kg / mm ² ) 13.3 13.1

From Tables 1, 2, and 3, the cured product of the polyphenol compound and / or the epoxy resin of the present invention showed a higher glass transition point and a lower water absorption rate than the cured product of the known epoxy resin composition.

[0061]

The epoxy resin composition using the polyphenols and / or the epoxy resin of the present invention is a cured product having excellent heat resistance and water resistance as compared with the epoxy resin composition which has been generally used conventionally. Give things. Therefore, it is extremely useful for a wide range of applications such as molding materials, casting materials, laminated materials, paints, adhesives, resists and the like.

Claims (7)

[Claims] 1. A formula (1): (In the formula, R and Q are a hydrogen atom, a halogen atom, and a carbon number of 1 to 1.
8 represents either an alkyl group or an aryl group, and individual P and Q may be the same or different from each other. ) Polyphenol compounds 2. An epoxy resin obtained by converting the phenolic hydroxyl group of the polyphenol compound of formula (1) according to claim 1 into a glycidyl ether. 3. An epoxy resin composition comprising (a) an epoxy resin (b) a polyphenol compound of formula (1) according to claim 1. 4. An epoxy resin composition comprising (a) the epoxy resin according to claim 2 and (b) a curing agent. 5. An epoxy resin composition comprising (a) the epoxy resin according to claim 2 and (b) the polyphenol compound of the formula (1) according to claim 1. 6. The method according to claim 3, 4 or 5 containing a curing accelerator.
The epoxy resin composition described. 7. A cured product obtained by curing the epoxy resin composition according to claim 3, 4, 5 or 6.