JPH11166038A - Alkyl-substituted polyphenols, epoxy resin and epoxy resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject polyphenol having a specific structure, useful as a curing agent for epoxy resin, etc., and giving a cured article having excellent heat-resistance, thermal expansion property, moisture absorptivity, soldering crack resistance and electrical characteristics. SOLUTION: The polyphenols are produced by introducing a structure of formula I (R1 is H or an alkyl, such as methyl, ethyl or propyl, a halogen such as chlorine or bromine or OH; R2 is an alkyl such as methyl, ethyl or propyl; (n) is 1-4; (m) is 2-4; (n) and (m) show the numbers of the groups R1 and R2 , respectively; (p) is 0-7). The polyphenols can be produced e.g. by condensing an alkyl-substituted xylylene compound of formula II (Q is a halogen such as chlorine or bromine, OH, an alkoxy such as methoxy or ethoxy or allyloxy) with phenolic compounds in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to alkyl-substituted polyphenols, epoxidized products thereof, and epoxy resin compositions containing the same.

[0002]

2. Description of the Related Art Hitherto, as polyphenols, phenol novolaks, cresol novolaks, higher alkyl-substituted novolaks, xylylenephenols called Zyloc, and the like have been known. In addition, these epoxides are also known.

[0003]

SUMMARY OF THE INVENTION The present invention relates to heat resistance,
An object of the present invention is to provide a phenol, an epoxy resin, and an epoxy resin composition containing the same, which are excellent in thermal expansion, moisture absorption, electrical properties, and the like.

[0004]

That is, the present invention provides (a)
The following equation (1)

[0005]

Embedded image

(Wherein R ₁ represents a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, a halogen atom such as chlorine or bromine or a hydroxyl group, and R ₂ represents a methyl group, an ethyl group or a propyl group, etc.) Each represents an alkyl group,
Each may be the same or different. n
Is an integer of 1 to 4; m is an integer of 2 to 4;
1 and the number of R2. p is an integer of 0-7. An alkyl-substituted polyphenol represented by the formula (2):

[0007]

Embedded image

(Wherein m, n, R ₂ and p have the same meaning as in formula (1). R ₃ is a hydrogen atom, a methyl group,
It represents an alkyl group such as an ethyl group or a propyl group, a halogen atom such as chlorine or bromine, a hydroxyl group or a glycidyloxy group, which may be the same or different.
G represents a glycidyl group. ) Epoxy resin,
(C) an epoxy resin obtained by reacting the alkyl-substituted polyphenols represented by the formula (1) with the epoxy resin represented by the formula (2); (d) the alkyl-substituted polyphenols according to the above (a) (E) an epoxy resin composition containing the epoxy resin described in (b) or (c) above and a curing agent, and (f) a curing agent comprising the above (a) The epoxy resin composition according to the above (e), which is the alkyl-substituted polyphenols according to the above item, and (g) a curing catalyst containing the above (d) to (d).
(F) The epoxy resin composition according to any one of the above items.
(H) An electronic component sealing composition according to any one of the above items (d) to (g), containing an inorganic filler.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The alkyl-substituted polyphenols of the present invention are, for example, represented by the following formula (3)

[0010]

Embedded image

(Q represents a halogen atom such as chlorine or bromine, an alkoxy group such as a hydroxyl group, a methoxy group or an ethoxy group, or an allyloxy group. R ₂ and m have the same meanings as in formula (1). )) And phenols can be condensed in the presence of an acid catalyst.

The compound represented by the above formula (3) includes
Examples include, but are not limited to, dimethylxylylene compounds, trimethylxylylene compounds, and tetramethylxylylene compounds where R ₂ is methyl. Examples of phenols include phenol, cresols, xylenols, alkylphenols such as ethylphenols or propylphenols, or halogeno-substituted phenols such as bromophenols, dibromophenols or chlorophenols, or catechol or resorcinol. Alternatively, diphenols such as hydroquinone can be mentioned, but the present invention is not limited thereto.

In the above condensation reaction, the amount of the phenol used is determined by the amount of the alkyl-substituted xylylene compound of the formula (3).
It is preferable to use the compound in an excess of at least twice the molar amount, preferably 2 to 10 times the molar amount. Acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid,
Polyphosphoric acid, hydrofluoric acid, toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, aluminum chloride, iron chloride, boron trifluoride and the like can be used. The amount of the compound used is preferably 0.1% of the alkyl-substituted xylylene compound of formula (3).
01 to 20% by weight. The reaction is not significantly affected, especially by the amount of acid catalyst used. The reaction temperature is usually 10 to
The temperature is 200 ° C, preferably 20 to 150 ° C.

In the reaction, a solvent may be used, or no solvent may be used. When a solvent is used, hydrocarbons such as toluene, xylene, hexane, and heptane; ethers such as diisopropyl ether and dioxane; alcohols such as methanol, ethanol, propanol, methyl cellosolve, and ethylene glycol; methyl ethyl ketone; methyl isobutyl ketone; Aprotic polar solvents such as ketones, dimethylformamide, dimethylsulfoxide and the like can be used.
0 times by weight is preferred. After the completion of the reaction, the acid catalyst is removed by neutralization or washing with water. Excess phenols can be removed by distillation or by dissolving in a solvent to obtain the alkyl-substituted polyphenols of the present invention.

The epoxy resin of the present invention can be reacted with an epihalohydrin such as epichlorohydrin from the alkyl-substituted polyphenols of the present invention using an alkaline substance such as caustic or alkali carbonate by a conventional method. . The usage ratio of the alkyl-substituted phenol and epihalohydrin is usually sufficient if the equivalent ratio is about 1: 1 to 1: 5, and may be used in excess. At this time, a high molecular compound is also slightly generated (about 5 to 10%). This corresponds to the epoxy resin described in the above item (d). Examples of the caustic alkali include caustic soda, caustic potash, lithium hydroxide and the like, and examples of the alkali carbonate include sodium carbonate, potash carbonate, baking soda and the like. The amount used is preferably equal to or slightly excess to the hydroxyl group in the alkyl-substituted polyphenols.

The reaction is carried out by reacting alcohols such as methanol, ethanol, isopropanol, butanol and methoxyethanol, ethers such as dioxane, diglyme, dibutyl ether and tetrahydrofuran; The reaction can be performed in an organic solvent such as a protic polar solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The amount used is usually 0.05 to 50 relative to epichlorohydrin.
It is by weight, preferably 0.1 to 20 times by weight. Also,
It is also possible to use a phase transfer catalyst in the reaction.

The reaction temperature is usually from 10 to 120 ° C, preferably from 30 to 90 ° C. The reaction is carried out using polyalkylphenols, epihalohydrin, and optionally the above organic solvent,
It is desirable to add the above-mentioned alkaline substance as it is or gradually as an aqueous solution while stirring the phase transfer catalyst. Further, it is preferable that water in the reaction system is distilled off by azeotropic dehydration. The reaction time can be from 1 to 10 hours. After the completion of the reaction, the used organic solvent and epihalohydrin are recovered, and salts of by-products that precipitate are removed by filtration or washing with water. At this time, a solvent which does not dissolve in water, such as an aromatic hydrocarbon, a ketone-based solvent, or an ether-based solvent, may be newly added.

After removing the salts, the solvent is distilled off to obtain the epoxy resin of the present invention. The target substance can be precipitated and removed by adding a poor solvent, cooling or the like.

The alkyl-substituted phenols of the present invention can be contained in an epoxy resin composition as a curing agent for an epoxy resin. The epoxy resin used in this case includes a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, an epoxidized 3,3 ′, 5,5′-tetramethylbiphenol, and an epoxy containing a naphthalene group. Compound, trisphenol-based epoxy resin, dicyclopentadiene-phenol-based epoxy resin, and the like. At this time, it is preferable to use an imidazole-based, phosphine-based, or tertiary amine-based curing catalyst. Further, as a curing agent, it is also possible to use in combination with a generally known curing agent such as phenol novolak, cresol novolak, or an aralkylene phenol resin known under the trade name of Xyloc. When used in combination, the proportion of the alkyl-substituted polyphenols of the present invention in the total curing agent is at least 10% by weight, preferably at least 20% by weight.

The epoxy resin of the present invention can be made into the epoxy resin composition of the present invention by combining it with a curing agent. As the curing agent used at this time, phenol novolak, cresol novolak, aralkylene phenol resin known under the trade name of Xyloc,
Naphthalene diols, bisphenols, biphenols, polyhydric phenols such as dicyclopentadiene-phenol resin, methylnadic acid, phthalic anhydride, acid anhydrides such as tetrahydrophthalic anhydride, diaminodiphenylmethane, diaminodiphenylsulfone, ethylenediamine, Examples include amines such as triethylenetetramine, amides such as dicyandiamide, and the alkyl-substituted polyphenols of the present invention. In this case, it is preferable to use an imidazole-based, phosphine-based, or tertiary amine-based curing catalyst.

In the epoxy resin composition of the present invention, the epoxy resin of the present invention may be a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, 3, 3, '5,
It is possible to use another epoxy resin such as an epoxidized 5′-tetramethylbiphenol, an epoxidized compound containing a naphthalene group, and a trisphenol-based epoxy resin. The other epoxy resin used in combination can be used in an amount of 10 to 90% by weight of the epoxy resin of the present invention.

In the epoxy resin composition of the present invention containing the alkyl-substituted polyphenols and / or the epoxy resin of the present invention, the curing agent is preferably used in an equivalent amount to the epoxy resin. 0.01 to 1 with respect to 100 parts by weight of the epoxy resin
Use 5 parts by weight.

Further, various compounding agents such as a silane coupling agent, a releasing agent and a pigment can be added to the epoxy resin composition of the present invention, if necessary.

When the epoxy resin composition of the present invention is used for encapsulating electronic parts, it is desirable to include an inorganic filler. As the inorganic filler, silica, alumina, titanium aluminum or the like having a spherical or crushed shape and an average particle diameter of 0.1 to 100 μm can be used. The inorganic filler is usually 6 in the epoxy resin composition.
It is used in a proportion occupying about 0 to 95% by weight, preferably about 75 to 90% by weight.

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 such as the epoxy resin of the present invention and a curing agent such as the alkyl-substituted polyphenols of the present invention, and, if necessary, a curing catalyst, an inorganic filler, and a compounding agent.If necessary, an extruder, a kneader, a roll, etc. The epoxy resin composition was sufficiently mixed until it became uniform, and then the epoxy resin composition was melted and molded using a casting or transfer molding machine, and then heated at 80 to 200 ° C. for 2 to 10 hours. By doing so, a cured product can be obtained.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 In a 300 ml four-necked flask, 25 g of 2,3,5,6-tetramethylxylylene glycol and 26 g of phenol were added.
9 g, methanesulfonic acid 0.7 g, ethanol 85 g
Was added to 80 ° C. to carry out a heating reaction for 5 hours. Then, 10 g of phenol was added thereto, and the mixture was further reacted for 5 hours, and cooled after completion of the reaction. Next, the formed precipitate is separated by filtration, washed with methanol and dried, and white α, α'-bis (4-hydroxyphenyl) -2,3,5,6-tetramethyl-
9.4 g of p-xylene (the alkyl-substituted polyphenols of the present invention) was obtained. Its melting point was 245 ° C. FIG. 1 shows the ¹ H-NMR spectrum. This NMR
The spectrum supports the structure of interest. The filtrate after obtaining the crystals was concentrated under the condition of 3 mmHg / 150 ° C. to obtain 25.1 g of a resinous material (solid when cooled). It contained high molecular weight compounds.

Example 2 In a 300 ml four-necked flask, 9 g of the alkyl-substituted polyphenols obtained in Example 1 and epichlorohydrin 2 were added.
4 g, dimethyl sulfoxide 10 g and water 0.4 g were charged and the temperature was raised to 55 ° C. Here is flaky caustic soda,
2.1 g was added in small portions over 1.5 hours. After completion of the addition, the reaction temperature was raised to 65 ° C, and the reaction was performed at 65 to 75 ° C for 2 hours. After the completion of the reaction, the mixture was cooled, and 50 ml of water and 50 g of methylisobutyl ketone were added thereto. The precipitate formed here was separated by filtration. Methanol was added to the methyl isobutyl ketone layer of the filtrate, and the formed precipitate was separated by filtration. The precipitates were combined to obtain 10.7 g of white crystals (the epoxy resin of the present invention). Incidentally, in order to identify the structure thereof, the compound was dissolved in dichloromethane, purified by a method of adding methanol and precipitating to obtain pure α, α'-bis (4-
(2,3-epoxypropyl) oxyphenyl) -2,
3,5,6-Tetramethyl-p-xylene was obtained. The melting point of this product by DSC was 150 ° C. FIG.
¹ shows a ¹ H-NMR spectrum. This supports the target structure described above.

Example 3 In a 300 ml four-necked flask, 25 g of 2,3,5,6-tetramethylxylylene glycol, o-cresol 3
0.9 g, methanesulfonic acid 1 g, methanol 85 g
Was added to 67 ° C. to carry out a heating reaction for 5 hours. 80 g of methyl isobutyl ketone was added thereto, and the mixture was heated and reacted for 4 hours while removing methanol. At the end of the reaction, the reaction temperature reached 95 ° C. A part of the reaction solution was taken, and a precipitate formed by adding methanol was filtered and dried. The ¹ H-NMR spectrum of the obtained white crystal was measured, and the main component was α, α′-bis (4-hydroxy-3-methylphenyl) -2,3,5,6-tetramethyl- It was confirmed to be p-xylenetetramethyl-p-xylene (the alkyl-substituted polyphenols of the present invention). According to the DSC measurement, it was found that heat absorption started at 120 ° C and the softening point was 120 ° C to 130 ° C. From the remaining reaction solution, methyl isobutyl ketone was distilled off by heating under reduced pressure.
44 g of a resinous material was obtained.

Example 4 Alkyl-substituted polyphenols 44 obtained in Example 3
g of epichlorohydrin and 50 g of dimethyl sulfoxide.
g and 2.5 g of water were charged and the temperature was raised to 60 ° C. To this, 8.4 g of flaky caustic soda was added little by little over 1.5 hours. After the addition was completed, the reaction temperature was raised to 65 ° C.
The reaction was carried out at 〜75 ° C. for 2 hours. After the completion of the reaction, 50 ml of water and 150 g of methylisobutyl ketone were added while heating,
After stirring and standing, the separated aqueous layer was removed. Concentrate the oil layer,
The residue was further added with 150 g of methyl isobutyl ketone and a 30% aqueous solution of caustic soda, and reacted at 70 ° C. for 2 hours. Then, the oil layer was washed twice with 50 ml of hot water, and the solvent was distilled off from the oil layer. 52.6 g were obtained. After a part of this was purified by the purification method described in Example 2 using dichloromethane and methanol, the ¹ H-NMR spectrum was measured. The results are shown in FIG. The NMR spectrum is
Supported the structure of α, α′-bis (3-methyl-4- (2,3-epoxypropyl) oxyphenyl) -2,3,5,6-tetramethyl-p-xylene. The melting point of this product by DSC was 160 ° C. The obtained epoxy resin has a softening point of 126 ° C., an ICI viscosity at 150 ° C. of 1.0 P, and an epoxy equivalent of 261 g / e.
q.

Example 5 The epoxy resin obtained in Example 4, an equivalent amount of phenol novolak having a softening point of 80 ° C. and triphenylphosphine as a curing catalyst were used in an amount of 1% by weight of the epoxy resin. Mix and mix at 160 ° C for 2 hours then 18
It was cured by heating at 0 ° C. for 4 hours. The glass transition point of the obtained cured product was 148 ° C. as measured by the DSC method. The weight increase ratio before and after immersing the cured product in water at 100 ° C. for 24 hours was 0.65%, which was an extremely low value. Its dielectric constant was 3.4.

[0032]

According to the present invention, there are provided novel alkyl-substituted polyphenols and epoxy resins which give cured products excellent in heat resistance, thermal expansion, moisture absorption, solder cracking resistance, electrical properties and the like. . These are useful because they can be used as a composition for electronic materials as a curing agent or an epoxy resin, respectively.

[Brief description of the drawings]

FIG. 1 shows α, α′-bis (4-hydroxyphenyl) -2,3,5,6-tetramethyl- obtained in Example 1.
¹ H-NMR spectrum of p-xylene

FIG. 2 shows the results of α, α′-bis (4-
(2,3-epoxypropyl) oxyphenyl) -2,
¹ H-N of 3,5,6, -tetramethyl-p-xylene
MR spectrum

FIG. 3 shows α, α′-bis (3-methyl-4- (2,3-epoxypropyl) oxyphenyl) -2,3,5,6-tetramethyl-p- obtained in Example 4. ¹ H-NMR spectrum of xylene

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (8)

[Claims] (1) The following formula (1): (Wherein R ₁ represents an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, or a propyl group, a halogen atom such as chlorine or bromine or a hydroxyl group, and R ₂ represents an alkyl group such as a methyl group, an ethyl group, or a propyl group. And each may be the same or different, and n is 1 to 4.
And m is an integer of 2 to 4, and R ₁ and R ₂ are respectively
Indicates the number of p is an integer of 0-7. ) Alkyl-substituted polyphenols represented by (2) The following formula (2): (In the formula, m, n, R ₂ and p represent the same meaning as in the formula (1). R ₃ represents a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, or a halogen atom such as chlorine or bromine. Represents a hydroxyl group or a glycidyloxy group,
They may be the same or different. G represents a glycidyl group. Epoxy resin represented by). 3. An epoxy resin obtained by reacting an alkyl-substituted polyphenol represented by the formula (1) with an epoxy resin represented by the formula (2). 4. An epoxy resin composition containing the alkyl-substituted polyphenols according to claim 1 as a curing agent. 5. An epoxy resin composition comprising the epoxy resin according to claim 2 and a curing agent. 6. The epoxy resin composition according to claim 5, wherein the curing agent is the alkyl-substituted polyphenol according to claim 1. 7. The epoxy resin composition according to claim 4, further comprising a curing catalyst. 8. The electronic component sealing composition according to claim 4, further comprising an inorganic filler.