JPH08319343A - Polyphenol compounds, epoxy resin, epoxy resin composition and its cured product - Google Patents

Abstract

PURPOSE: To obtain a polyphenol compound having a specific structure, useful as an epoxy resin-curing agent giving epoxy resin cured products excellent in heat resistance, water resistance and toughness, and further useful as a raw material for the epoxy resins giving the cured products. CONSTITUTION: This polyphenol compound has a structure of the formula (n is a positive number; R1 , R2 are H, methyl, but when one of the R1 , R2 is H, the other is methyl; P is H, a halogen, a 1-8C alkyl, an aryl). The compound is obtained e.g. by subjecting an allylphenol compound and the other phenol compound to a condensation reaction in the presence of a catalyst. The reaction is preferably performed by using 1 mole of the allylphenol compound and 0.1-4 moles of the other phenol compound at 80-150 deg.C. The reaction time is usually 0.5-10 hrs. The catalyst is preferably boron trifluoride, its complex with an ether compound, and anhydrous aluminum chloride. In order to obtain an epoxy resin from the compound of the formula, the compound of the formula is preferably reacted with an epihalohydrin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin curing agent, an epoxy resin and an epoxy resin composition which give a cured product excellent in heat resistance, water resistance and toughness, and a cured product thereof.

[0002]

2. Description of the Related Art Heretofore, epoxy resin compositions containing an epoxy resin, a phenol novolac resin, and a curing accelerator as main components have been widely used in the fields of electric / electronic parts and IC encapsulants. The high density and high integration of ICs in recent years have required the sealing materials to have high heat resistance, low water absorption, and high toughness. In particular, the harsh condition of immersion in a solder bath in high-density mounting of ICs further increases the demand for cured products with high heat resistance, low water absorption, and high toughness.

[0003]

However, in the conventional epoxy resin composition, the cresol novolac type epoxy resin generally used as an epoxy resin has high heat resistance, but improvement in water absorption and toughness is required. Has been.

On the other hand, the phenol novolac resin, which is generally used as a curing agent, is still insufficient in heat resistance and does not give satisfactory results under the above-mentioned conditions which are becoming more and more severe. Therefore, development of a resin that gives a cured product having excellent properties such as heat resistance, water absorption, and toughness has been awaited.

[0005]

In view of these circumstances, the present inventors have earnestly studied for an epoxy resin composition which gives a cured product excellent in heat resistance, water resistance and toughness, and as a result, have a specific molecular structure. The present invention was completed by finding that an epoxy resin composition containing a polyphenol and an epoxy resin obtained by epoxidizing the same imparts excellent heat resistance, water resistance and toughness to the cured product. Came to let.

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

Embedded image

(In the formula (1), n represents a positive number, and R ₁ , R
₂ represents a hydrogen atom or a methyl group, and when either one is a hydrogen atom, the other is a methyl group. P represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group, and each P may be the same as or different from each other. (2) Formula (2)

[0008]

[Chemical 4]

(In the formula (2), n, R ₁ , R ₂ , and P have the same meanings as in the formula (1), and G represents a glycidyl group.) (3) (A) Epoxy resin (b) Epoxy resin composition containing the polyphenol of formula (1) described in (1) above, (4) (a) Epoxy resin of formula (2) described above in (2) (B) Epoxy resin composition containing a curing agent,

(5) (a) Epoxy resin of formula (2) described in (2) above (b) Epoxy resin composition containing polyphenols of formula (1) described above in (1), (6) ) The epoxy resin composition according to the above (3), (4) or (5) containing a curing accelerator, (7) above (3), (4) containing an inorganic filler.
(5) or (6) described epoxy resin composition, (8) a cured product obtained by curing the above (3), (4), (5), (6) or (7) epoxy resin composition Is provided.

In the formula (1), n represents a positive number, preferably 0.01 to 10 and particularly preferably 0.05 to 5. The compound represented by the formula (1) can be obtained, for example, by subjecting allylphenols and other phenols to a condensation reaction in the presence of a specific catalyst.

The compound represented by the formula (2) can be obtained, for example, by reacting the compound represented by the formula (1) with epihalohydrin in the presence of an alkali metal hydroxide.

Here, the allylphenols correspond to compounds having at least one allyl group and at least one phenolic hydroxyl group. For example, allylphenol, allylcresol, allylethylphenol, allyl-n-propylphenol, allylisobutylphenol, allyl. -T-
Examples thereof include various o-, m-, p-isomers such as butylphenol, allyloctylphenol, allylnonylphenol, allylxylenol, allylmethylbutylphenol, allyl-di-t-butylphenol and the like. These allylphenols may be used alone or in combination of two or more.

The phenols are compounds having at least one phenolic hydroxyl group other than the above allylphenols, and examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol and octylphenol. , Nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, and various o-, m-, p-isomers of alkylphenol, or cycloalkylphenol typified by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, and the like. , Or substituted phenols such as phenylphenol. These phenols may be used alone or in combination of two or more.

When the above condensation reaction is carried out, the amount of the phenols used is usually 0.1 per mol of allylphenols.
It is in the range of 01 to 5 mol, preferably 0.1 to 4 mol.

An acid catalyst is usually used in the above condensation reaction. Although various kinds of acid catalysts can be used, Lewis acids such as boron trifluoride (or a complex thereof with ethers), anhydrous aluminum chloride, zinc chloride, sulfuric acid and titanium chloride are preferable, and boron trifluoride is particularly preferable. (Or a complex of this and ethers), anhydrous aluminum chloride is preferable. The acid catalyst may be used alone or in combination of two or more kinds. The amount of these acid catalysts to be used is not particularly limited, but can be selected in the range of 0.001 to 0.1 times the mole of allylphenol. When adding these acid catalysts to the reaction mixture, they should be added to the heated melt of the phenols beforehand, or diluted with an appropriate solvent (for example, a solvent inert to the reaction described below) and added gradually. It is also possible to do so.

Since many of the phenols used in this reaction are easily oxidized, it is preferable to purge the inside of the reaction vessel with nitrogen gas or the like during a series of reaction operations.
Furthermore, this condensation reaction is often accompanied by a large amount of heat generation, so the above acid catalyst is usually added to the heated melt or solvent melt of phenols in advance, and allylphenols are introduced into the reaction vessel while checking the reaction temperature. Preferably.

The condensation reaction is preferably carried out in the range of 40 to 180 ° C., particularly preferably in the range of 80 to 150 ° C., and the reaction time can usually be selected in the range of 0.5 to 10 hours. . These reactions can also be carried out in the presence of a solvent inert to the reaction such as toluene, nitrobenzene, diphenyl ether, dichlorobenzene, carbon disulfide. The amount of the solvent used is usually 50 to 300% by weight based on the total weight of the charged raw materials, and 100 to 25
0% by weight is preferred. Further, the reaction product thus obtained is subjected to neutralization treatment so as to be neutral, or after repeated washing with water in the presence of a solvent, water is separated and drained, and then the solvent and unreacted products are removed under heating and reduced pressure. As a result, the polyphenols of the present invention represented by the formula (1) are obtained. (Hereinafter, simply referred to as polyphenols unless otherwise specified).

As a method for obtaining the epoxy resin of the present invention represented by the formula (2) from polyphenols, a known method can be adopted. For example, sodium hydroxide, potassium hydroxide or another alkali metal hydroxide is added all at once to a dissolved mixture of the obtained polyphenols and excess epichlorohydrin or epihalohydrin such as epibromhydrin, or 20 to 120 ° C. while being added. The epoxy resin of the present invention can be obtained by reacting at the temperature of 1 to 10 hours.

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 the aqueous solution of the alkali metal hydroxide is continuously added to the reaction mixture. Alternatively, water and epihalohydrin may be continuously distilled off under reduced pressure or atmospheric pressure, and liquid separation may be performed to remove water and epihalohydrin may be continuously returned to the reaction mixture.

Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of polyphenols and epihalohydrin, and the mixture is reacted at 50 to 150 ° C. for 1 to 5 hours. Alternatively, a solid or aqueous solution of an alkali metal hydroxide may be added to the resulting halohydrin etherified product of polyphenols, and the mixture may be reacted again at a temperature of 20 to 120 ° C. for 1 to 10 hours for dehydrohalogenation (ring closure).

The amount of epihalohydrin used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, based on 1 equivalent of hydroxyl groups of polyphenols. The amount of the alkali metal hydroxide used is 0.8 to 1.5 mol, preferably 0.9, relative to 1 equivalent of the hydroxyl group of the polyphenols.
~ 1.1 mol. Furthermore, in order to make the reaction proceed smoothly, in addition to alcohols such as methanol and ethanol,
It is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide.

When alcohols are used, the amount thereof is usually 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. When an aprotic polar solvent is used, it is usually 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of epihalohydrin.

After washing these reaction products of the epoxidation reaction with or without washing with water, heating under reduced pressure at 100 to 250 ° C.
Epihalohydrin, solvent, etc. are removed at a pressure of 10 mmHg or less. To obtain an epoxy resin having less hydrolyzable halogen, the obtained 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, based on 1 equivalent of the hydroxyl group of the polyphenol used in the epoxidation,
It is particularly preferably 0.05 to 0.2 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 polyphenols of the present invention as an essential component, and further adding a curing accelerator and the like if necessary. (3), (5),
In the epoxy resin composition of the present invention described in (6) and (7), the polyphenols of the present invention can be used alone or in combination with other curing agents. When used in combination, the proportion of the polyphenols of the present invention in the total curing agent is preferably 30% by weight or more, and particularly preferably 40% by weight or more. Specific examples of the curing agent that can be used in combination with the polyphenols of the present invention include diaminediphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, amine compounds such as dicyandiamide, dimer of linolenic acid and ethylenediamine. Synthesized polyamide resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride acid,
Novolak resins such as phenol novolac and cresol novolac and modified products thereof, imidazole, BF ₃
-Amine complexes, guanidine derivatives 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), (6) and (7), the epoxy resin of the present invention is used alone or in combination with another epoxy resin as the component (a). Can be used. When used together,
The proportion of the epoxy resin of the present invention in all epoxy resins is preferably 30% by weight or more, and particularly preferably 40% by weight or more. In this case, the epoxy resin used is usually 1
Examples thereof include compounds having two or more epoxy groups in the molecule, and there is no particular limitation as long as they are generally used for electronic devices. Specific examples of epoxy resins that can be used include phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolac type epoxy resins and other novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxies. Resins, bisphenol S type epoxy resins, bisphenol I type epoxy resins, biphenyl type epoxy resins and other epoxy resins obtained from aromatic dihydric phenols, glycidyl obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epihalohydrin Ester type epoxy resins, glycidyl amine type epoxy resins obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epihalohydrin can be mentioned. . These epoxy resins may be used alone or in combination of two or more.

In the epoxy resin composition described in (3), (6) and (7), examples of the epoxy resin as the component (a) include the epoxy resins of the present invention and the other epoxy resins. In addition, in the epoxy resin compositions described in (4), (6), and (7), examples of the curing agent as the component (b) include the polyphenols of the present invention and the other curing agents.

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 epoxy groups of the epoxy resin. When the amount is less than 0.7 equivalent based on 1 equivalent of epoxy group,
Alternatively, if it exceeds 1.2 equivalents, the curing may be incomplete in any case, 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 the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo ( Examples include tertiary amines such as 5,4,0) 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 optionally contains an inorganic filler. Specific examples of the inorganic filler that can be used include silica, alumina, talc and the like. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention, if necessary. Furthermore, various compounding agents such as a silane coupling agent, a release agent and a pigment can be added to the epoxy resin composition of the present invention, if necessary.

The epoxy resin composition of the present invention can be 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, an epoxy resin (component (a)), a curing agent (component (b)), a filler and other compounding agents are used, if necessary, until uniform using an extruder, a kneader, a roll or the like. The epoxy resin composition is sufficiently mixed to obtain an epoxy resin composition, which is melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to cure the epoxy resin composition. You can get things.

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 and the like. A prepreg obtained by impregnating the base material with heat and drying can also be hot-press molded to obtain a cured product. At this time, the solvent is used in an amount such that the proportion of the solvent in the mixture of the epoxy resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 65% by weight.

[0034]

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.

Example 1 A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 47 parts of phenol and 1 part of boron trifluoride diethyl ether complex, and at room temperature while blowing nitrogen. It was stirred. Then, in an oil bath at 80 ° C
The mixture was heated up to 134 parts of 2-allylphenol over 2 hours, and further reacted at 120 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, 400 parts of toluene and 50 parts of 20 wt% sodium dihydrogen phosphate aqueous solution were added, and the mixture was transferred to a separating funnel and washed with water. After washing with water until the wash water shows neutral,
Unreacted phenol, allylphenol and solvent were removed from the organic layer under reduced pressure by heating, and the following formula (3)

[0036]

Embedded image

(In the formula (3), n, R ₁ and R ₂ are represented by the formula (1)
Has the same meaning as in. )

There were obtained 124 parts of the polyphenol (A) of the present invention represented by: The obtained polyphenols had a softening point of 70.1 ° C. and a hydroxyl group equivalent of 121 g / eq.

Example 2 Polyphenols (A) 121 was added to a flask equipped with a thermometer, a cooling tube and a stirrer while purging with nitrogen gas.
Parts, 370 parts of epichlorohydrin, and 92.5 parts of dimethyl sulfoxide were charged and dissolved. The mixture was further heated to 45 ° C., 40.4 parts of flaky sodium hydroxide (purity 99%) was added portionwise over 90 minutes, and then the mixture was further reacted at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After the reaction, 130 ℃
Then, dimethylsulfoxide and epichlorohydrin were distilled off under reduced pressure with heating, and 354 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 wt% sodium hydroxide aqueous solution 1
After adding 0 part and reacting for 1 hour, washing with water was repeated 3 times to make the pH of the washing solution neutral. Further, the water layer is separated and removed, and methyl isobutyl ketone is distilled off from the oil layer under reduced pressure by heating using a rotary evaporator to obtain a compound represented by the following formula (4).

[0041]

[Chemical 6]

(In the formula (4), n, R ₁ and R ₂ are represented by the formula (1)
Has the same meaning as in, and G represents a glycidyl group. )

The epoxy resin (B) 1 of the present invention represented by
66 parts were obtained. The softening point of the obtained epoxy resin is 51.
The epoxy equivalent was 189 g / eq at 2 ° C.

Example 3 54 parts of o-cresol instead of phenol, 2-allyl-6-cresol 1 instead of 2-allylphenol
The reaction was carried out in the same manner as in Example 1 except that 48 parts were used, and the following formula (5)

[0045]

[Chemical 7]

(In the formula (5), n, R ₁ and R ₂ are represented by the formula (1)
Has the same meaning as in. )

There were obtained 141 parts of the polyphenols (C) of the present invention represented by: The hydroxyl equivalent of the obtained polyphenols is 133 g / eq and the softening point is. It was 75.3 ° C.

Example 4 An epoxidation reaction was carried out in the same manner as in Example 2 except that 133 parts of polyphenol (C) was used, and the following formula (6) was used.

[0049]

Embedded image

(In the formula (6), n, R ₁ and R ₂ are represented by the formula (1)
Has the same meaning as in, and G represents a glycidyl group. )

The epoxy resin (D) 1 of the present invention represented by
76 parts were obtained. The softening point of the obtained epoxy resin is 53.
The epoxy equivalent was 204 g / eq at 1 ° C.

Examples 5 to 9 and Comparative Example 1 In Examples 5 to 6, the epoxy resin was replaced with the o-cresol type epoxy resin EOCN1020 (epoxy equivalent 200 g /
eq, manufactured by Nippon Kayaku Co., Ltd., and curing using polyphenols (A) and (C) as curing agents and epoxy resins (B) and (D) as epoxy resins as Examples 7 to 8. Phenol novolac as an agent (hydroxyl equivalent 106g / e
q, manufactured by Nippon Kayaku Co., Ltd., epoxy resin (D) was used as the epoxy resin in Example 9, polyphenols (A) was used as the curing agent, and EO was used as the epoxy resin in Comparative Example 1.
CN1020, phenol novolac as a curing agent, and triphenylphosphine (TP) as a curing accelerator.
P), stearic acid as a compounding agent, a silane coupling agent, and silica powder as an inorganic filler in the composition shown in the composition column of the compound in Table 1, and kneaded with a roll at 70 ° C. for 15 minutes to obtain 150 1 at ℃ and molding pressure of 50 kg / cm ² .
Transfer molding is performed for 80 seconds, the semiconductor element is resin-sealed, and then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours, and these are cured at 80 ° C. for 2 hours and then 120
After curing for 2 hours at ℃ and 5 hours at 200 ℃, assemble a simulated semiconductor device, heat cycle test, and PCT
The test was conducted. Heat cycle test: -50 ° C / 5 min
A temperature cycle test was performed 2000 times at 150 ° C. for 5 minutes, and in the PCT test, the simulated semiconductor device was left in a pressure cooker state (121 ° C. × 2 atm × 100% RH) and the number of aluminum corrosion occurrences was measured. In the table, the numerical values in the composition column of the formulation represent parts.

[0053]

[Table 1] Table 1 Actual Examples Comparative Examples 5 6 7 8 9 1 Composition of Composition EOCN1020 180 180 180 Polyphenols (A) 109 107 Epoxy Resin (B) 180 Polyphenols (C) 120 Epoxy Resin (D) 180 180 Phenol novolac 101 94 95 TPP 1.8 1.8 1.8 1.8 1.8 1.8 Silica powder 800 800 800 800 800 800 Stearic acid 4 4 4 4 4 4 Silane coupling agent 5 5 5 5 5 5 Physical properties of cured product Heat cycle test 4/20 5 / 20 1/20 0/20 0/20 14/20 PCT (1000hr) 0/20 0/20 0/20 0/20 0/20 18/20

In Table 1, the results of the heat cycle test were conducted on X1 samples, and the number X2 of samples in which aluminum corrosion occurred was indicated by X2 / X1. Also, PCT
The results of the test were tested on Y1 samples, and the number Y2 of samples in which aluminum corrosion occurred was represented by Y2 / Y1. Table 1
As is clearer, the cured product obtained by using the epoxy resin composition of the present invention has excellent heat resistance, water resistance, and toughness as compared with the conventional epoxy resin and the curing agent, and as a result, the obtained cured product is obtained. It has the characteristic that the reliability of the product is high.

[0055]

INDUSTRIAL APPLICABILITY The polyphenols or epoxy resins of the present invention can give a cured product having excellent heat resistance, water resistance and toughness, and the reliability of the cured product obtained as a result is improved. Materials, laminated materials, paints, adhesives,
It is extremely useful for a wide range of applications such as resists.

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Claims (8)

[Claims] 1. A formula (1): (In the formula (1), n represents a positive number, and R ₁ and R ₂ represent a hydrogen atom or a methyl group. When either one is a hydrogen atom, the other is a methyl group. P is hydrogen. An atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and the individual P's may be the same or different from each other.). 2. Formula (2): (In the formula (2), n, R ₁ , R ₂ and P have the same meanings as in the formula (1), and G represents a glycidyl group.). 3. An epoxy resin composition comprising (a) an epoxy resin and (b) a polyphenol of formula (1) according to claim 1. 4. An epoxy resin composition comprising (a) an epoxy resin of the formula (2) according to claim 2 and (b) a curing agent. 5. An epoxy resin composition comprising (a) an epoxy resin of the formula (2) according to claim 2 and (b) a polyphenol of the formula (1) according to claim 1. 6. The epoxy resin composition according to claim 3, 4 or 5 containing a curing accelerator. 7. The epoxy resin composition according to claim 3, 4, 5 or 6 containing an inorganic filler. 8. A cured product obtained by curing the epoxy resin composition according to claim 3, 4, 5, 6 or 7.