JPS59227873A - Preparation of glycidyl ether of polyhydric phenol - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by condensing a phenol with a halogenated hydrocarbon in the presence of a Friedl-Crafts catalyst, treating the condensation product with a polyhydric phenol, reacting the resultant product with an epihalohydrin. CONSTITUTION:A phenol consisting of 0-100mol% compound shown by the formula I , 0-100mol% compound shown by the formula II, and 0-80mol% compound shown by the formula III (with the proviso that total amounts of the compounds shown by the formula I -formula III are 100mol%, R1-R6 are H, 1-8C alkyl, aromatic group, or halogen; R6-R8 are 1-10C alkyl, aromatic group, halogen, etc.) is condensed with a compound shown by the formula IV (n is 2- 12; m is 2n-2 or 2n; X is halogen) in the presence of a Friedel-Crafts catalyst, to give a condensation product, which is reacted with an aldehyde in the presence of an acid catalyst to give a polyhydric phenol, which is reacted with an epihalohydrin to give the desired substance. EFFECT:A small amount of impurity ions are produced, and a compound capable of providing a cured material having improved heat resistance and flexibility is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glycidyl ether of polyhydric phenol, which produces a small amount of impurity ions and can provide a cured product with excellent heat resistance and flexibility.

More specifically, the present invention has a low content of hydrolyzable chlorine, which causes the generation of impurity ions after curing, and has a glass transition temperature higher than that of conventional heat-resistant epoxy, despite having a low elastic modulus. It is.

In recent years, as semiconductor elements in electronic components such as large-scale integrated circuits have become denser and larger, there has been an increasing demand for improved reliability. Resin sealing is used for packages of semiconductor devices because it is inexpensive and can be mass-produced. This thermosetting resin for sealing is required to first have a low amount of hydrolyzable chlorine and secondly to have low stress applied to semiconductor elements. The latter requirement requires that the cured product have a low elastic modulus.

In order to obtain a cured product with a low elastic modulus, it has been considered to add a flexibility imparting agent to the glycidyl ether of cresol novolac, but this lowers the glass transition temperature of the cured product and reduces its heat resistance. It has also been considered to add a butadiene-acrylonitrile copolymer having functional groups at both ends of the molecule, but this has problems such as deterioration of electrical properties and reduction of insulation resistance.

Various glycidyl ethers of polyhydric phenols have been developed as a method for obtaining a cured product with a low elastic modulus, but all of them lower the glass transition temperature of the cured product and reduce its heat resistance. Further, no material has been obtained that satisfies the other required property for sealing materials, which is a low content of hydrolyzable chlorine. For example, Japanese Patent Publication No. 51-41919 describes that glycidyl ether of polyhydric phenol obtained by the reaction of 1°2-polybutadiene and phenol has good flexibility. However, according to Example 1 of the patent, the heat distortion temperature, which is correlated with the glass transition temperature, is about 80° C. lower than that of a commercially available solid cured product whose main ingredient is glycidyl ether of bisphenol A. The heat distortion temperature of this cured product based on solid glycidyl ether of bisphenol A is approximately 40°C higher than the heat distortion temperature of a cured product based on glycidyl ether of cresol novolak, which is generally used for sealing materials. low. As described above, generally speaking, increasing the glass transition temperature and lowering the elastic modulus are contradictory physical properties required.

As a result of intensive research into a method for producing glycidyl ether of polyhydric phenol that satisfies the above requirements, especially as a packaging material for electronic components of large-scale integrated circuits, the present inventors have discovered that polyhydric phenol can be produced by condensation from phenols. The present invention has been achieved by discovering that such objects can be achieved by using a specific condensing agent.

That is, the present invention provides (1) phenols consisting of 0 to 100 mol% of the compound represented by the general formula, θ to 100% of the compound represented by the general formula, 0 to 80 mol% of the compound represented by the general formula Oyohi; However, the total of (I) to @) is 100 mol%. In the formula, R1-R6 are the same or different groups selected from a hydrogen atom, a hydroxyl group having 1 to 8 carbon atoms, an aromatic group, and a halogen atom, and R6-R8 are the same or different groups having 1 to 8 carbon atoms.
They are the same or different groups selected from 10 alkyl groups, aromatic groups, aryl groups, and halogen atoms. ) general formula % formula %) (wherein n is an integer from 2 to 12, m is 2n-2 or 2n, and X is a halogen atom). (i) React the condensate and aldehydes in the presence of an acid catalyst to form a polyhydric phenol; (=) the polyhydric phenol and epihalohydrin; This is a method for producing glycidyl ether of polyhydric phenol, which involves reaction and glycidyl etherification. Hereinafter, specific examples of the detailed explanation of the present invention include phenol, m-cresol, m-ethylphenol, m-isopropylphenol, 8-n-propylphenol, 8-chlorophenol, 8-bromophenol, 8.5 -xylenol, 8.5-dichlorophenol, 8-chloro, 5-methylphenol, etc., but the scope of the present invention is limited to these, propenylphenol,
0-benzylphenol, $-n-amyl-m-cresol, 0-cresol, p-cresol, 0-ethylphenol, P-phenylphenol, p-t-pentylphenol, p-t-butylphenol, O-chlorophenol , 4-chloro-8,5-xylenol, 0-
Although the scope of the present invention is limited to allylphenol, nonylphenol, 0-bromophenol, 4-methylphenol, 2.4-
Examples include xylenol, 2.6-xylenol, 2.4 dichlorophenol, 2.4 dibromophenol, dichloroxylenol, dibromoxylenol, 2°4.5-trichlorophenol, 6-phenyl-2-chlorophenol, etc. However, the scope of the present invention is not limited thereto.

The phenols in the present invention include 0 to 100 mol% of the compound represented by general formula (1), 0 to 100 mol% of the compound represented by general formula (1)), and 0 to 80 mol% of the compound represented by general formula (2). It consists of mol%. However, the total of (I) to (2) is 100 mol%.

The above phenols are represented by the general formula (transformation)
) is reacted with y'-ionized JiJ hydrogen hydride in the presence of a Friedel-Crafts catalyst to form a condensate. A method for condensing phenols and the compound of general formula (g) using a Friedel-Crafts catalyst is described by G. A. 0LAII // FRIEDE
L-CRAFT8 AND RELATED R
A method such as that described in EAOTION 8* can be applied. Specifically, phenols and the compound of general formula (3) can be condensed to form a condensate using a metal halide catalyst. Specific examples of the compound represented by the general formula (transformation) of the present invention include 1.2-dichloroethane, 1.
2-dichloropropane, 2,8-dichloro-2-methylbutane% 1.8-dichloropropane, 1.4-dichlorobutane, 2°8-dichlorobutane, 8.4-dichloro-
1-butene, 1,4-dichloro-2-butene, 1゜5-
Dichlorpenkun, 1.8-dichlorpropene, 2.8
-dichloro-1-propene, dichlorocyclooctane, etc., but the scope of the present invention is not limited thereto.

The condensate thus obtained and aldehydes are further condensed using an acid catalyst. The production method used here can be a commonly used production method for novolac type phenolic resins, and may be a batch method or a continuous method as described in JP-A-51-180498. An example of a manufacturing method is as described in the section on phenolic resins on page 1 of Vol. 10 of the Encyclopedia of Polymer Science and Technology (Interscience Haflishers). j Inorganic acids such as phosphoric acid and sulfuric acid or organic acids such as p-toluenesulfonic acid and oxalic acid are combined with M[, and the condensate obtained from phenols and the compound of the general formula (transformation) is reacted with aldehydes. Use polyhydric phenol.

Specific examples of aldehydes used in the method for producing glycidyl ether of polyhydric phenol of the present invention include formaldehyde, acetaldehyde, and phenylacetaldehyde, but the scope of the present invention is not limited thereto.

In order to convert the polyhydric phenol thus obtained into glycidyl ether, a method commonly used for producing glycidyl ether from -hydric or polyhydric phenol can be applied. For example, +, f, polyhydric phenols are dissolved in epihalohydrin, an aqueous alkali metal hydroxide solution is continuously added to this solution, water and epihalohydrin are distilled from the reaction mixture, and the distilled liquid is separated into water. A manufacturing method can be used in which the layer is removed and the epihalohydrin is returned to the reaction system. Note that this reaction can also be carried out in the presence of a cyclic or linear ether. Specific examples of ether compounds include dioxane and jetoxyethane, but the scope of the present invention is not limited thereto. Specific examples of epihalohydrin include epichlorohydrin and ebibromohydrin, and epichlorohydrin is preferred because of its industrial ease of availability.

The main component is the glycidyl ether of polyhydric phenol of the present invention, which includes phenol novolak, diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, phthalic anhydride, tetrahydrofucuric anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride. Hardening agents such as silica, alumina, talc,
Inorganic fillers such as clay and glass fiber, curing accelerators such as imidazoles, tertiary amines, and phenols, internal mold release agents such as stearic acid, calcium stearate, calcuba wax, and montan wax, and as required. A composition containing a flame retardant imparting agent such as glycidyl ether of tetrabromobisphenol can be suitably used as a material for the electrical and electronic industries, particularly as a sealant for integrated circuits.

The amount of curing agent, filler, curing accelerator, and internal mold release agent varies depending on the type, but as a general rule, the amount of curing agent is equivalent to the number of moles of the epoxy group in the glycidyl ether of the novolac-type substituted phenol. The blending amount is such that the number of moles of the functional group is equal to the number of moles of the filler, the blending amount is such that the filler is almost close packed with respect to the volume of the total blending amount, the blending amount of the curing accelerator is about the catalytic amount, and the internal The mold release agent is used in an amount of about 0.2 to 2.0% by weight based on the total amount of the mold release agent.

The glycidyl ether of polyhydric phenol obtained by the method of the present invention provides a cured product with a lower elastic modulus than the conventional glycidyl ether of orthocresol novolac or glycidyl ether of phenol novolak, and prevents a decrease in the glass transition temperature. The content of hydrolyzable chlorine is low.

The present invention will be explained below with reference to Examples, but the present invention is not limited to the Examples. The epoxy equivalent as used in the present invention is defined as Durham equivalent per mole of glycidyl ether group.

Hydrolyzable chlorine is the chlorine ion released when glycidyl ether of polyhydric phenol is dissolved in dioxane and an alcoholic solution of potassium hydroxide is heated under reflux for 80 minutes, which is determined by back titration with a silver nitrate solution. It is defined by the weight percentage of chlorine atoms in a compound.

Example 1 (1) Synthesis of polyhydric phenol A 1-ton vessel equipped with a thermometer, cooling tube, dropping funnel, and stirrer
1.0 mol of orthocresol and 1.5 mol of aluminum chloride as a catalyst were placed in a flask and thoroughly stirred.

2.0 mol of 1,2 dichloroethylene was added dropwise over about 1 hour while maintaining the system temperature at 60 to 80°C, and the temperature was raised to about 80°C.
It was kept warm for 2 hours. Next, the reaction mixture was added little by little to water, the resulting resin was extracted with methyl isobutyl ketone, the solution was thoroughly washed with water, methyl isobutyl ketone and unreacted substances were removed, and orthocresol and 1.2 dichloromethane were added. An ethylene condensate was obtained.

1.0 mol of this condensate (as phenolic hydroxyl group)
0.01 mol of p-toluenesulfonic acid was added as a catalyst, and the mixture was melt-mixed at a temperature of 100°C. 0.8 mol of formalin aqueous solution (as formaldehyde) was added dropwise over about 2 weeks, and then kept warm for 8 hours. The catalyst acid was neutralized with sodium hydroxide and the aqueous phase was dispersed.

After further washing with water, the mixture was heated to remove residual moisture by distillation, and then heated under reduced pressure to 150° C. to remove volatile components. The condensate obtained at this time was a reddish-brown polyhydric phenol that was solid at room temperature.

(2) Synthesis of glycidyl ether of polyhydric phenol 1 ton equipped with thermometer, separation tube, dropping funnel, and stirrer
In a flask, add 1.0 mol of the polyhydric phenol obtained in (1) (the phenolic hydroxyl group is mixed with 7.0 mol of epichlorohydrin).
Dissolve in moles.

The temperature was maintained at 64° C. and the pressure was 1504 Kf, and a 48% NaOH aqueous solution was continuously added over 6 hours.

Between the seeds, epichlorohydrin and water were azeotropically liquefied and separated into an organic layer and an aqueous layer in a separation tube, the aqueous layer was removed from the system and the organic layer was circulated into the system.

After completion of the reaction, the mixture was kept warm for 1 hour to evaporate and remove unreacted epichlorohydrin, and the reaction product was dissolved in methyl isobutyl ketone. Next, after the by-product salt was separated, methyl isobutyl ketone was removed by evaporation to obtain a solid resin at room temperature. The softening point of this resin was 88°C. Softening point is JIS-2
It was measured by 8δ1 (petroleum asphalt softening point test method (ring and ball method)). The epoxy equivalent weight was 206 and the hydrolyzable chlorine was 0.07 wt%. The average number of phenyl nuclei calculated from the GPO curve was 5.8.

(8) Glycidyl polyhydric phenol obtained in viscoelasticity measurement Q) of cured product) 1.0 mol of ether (as an epoxy group, specifically 20
69), 1.0 mol of phenol novolac (as phenolic hydroxyl group), and 0.8 mol of curing accelerator based on the total amount.
Parts by weight of Tris÷dimethylaminomethyl÷pheno-J (manufactured by Sumitomo Chemical Co., Ltd., Sumikia D) were roll-kneaded to prepare a composition. Next, this composition was molded into a 1+im sheet by pressurizing and heating. A cured molded product was prepared by post-curing the molded product at 170° C. for 5 hours. The results of measuring the viscoelasticity of this molded product are shown in FIG.

It can be seen that the elastic modulus is lower than that of the glycidyl ether of cresol novolak in Comparative Example 1. Furthermore, compared to the glycidyl ether of polyhydric phenol shown in Comparative Example 2, the glycidyl ether of polyhydric phenol of Example 1 has a similar elastic modulus, but the glass transition temperature (temperature at the peak point of α dispersion). ) is about 20°C higher.

As described above, the glycidyl ether of polyhydric phenol obtained by the method of the present invention has excellent properties such as a high elastic modulus and a high glass transition temperature of 201°C, so that it can be used as a main agent for sealing integrated circuits. In general, fillers, internal mold release agents, pigments, and the like are used in combination in addition to the base agent, curing agent, and curing accelerator in the formulation of encapsulants for integrated circuits.

Although these materials were not blended here for the purpose of clarifying the characteristics of the base resin, the properties of the base resin shown here are maintained even in a cured product containing these materials.

Further, the hydrolyzable chlorine content was 0.07 wt%, which also satisfies the purity required as a sealant for integrated circuits.

Comparative Example 1 Commercially available glycidyl ether of cresol novolak (Sumi Epoxy E8CN-220 manufactured by Sumitomo Chemical Co., Ltd.)
) was used as the main ingredient, and a cured molded product was prepared in the same manner as in Example 1 (8).

The results of measuring the viscoelasticity of this molded product are shown in FIG.

An elastic modulus lower than this cured molded product is desired in the market as a sealant for integrated circuits, and the polyhydric phenol glycidifrether of Example M1 satisfies this requirement. Further, the glass transition temperature of the molded product of Comparative Example 1 is 208° C. from FIG. 1.

Comparative Example 2 OJresocreso, which is the intermediate product of Example 1 (1)
JL/(!11) A glycidyl ether of a polyhydric phenol was obtained by the method (2) of Example 1 using a condensate of 2 dichloroethylene as a raw material for a polyhydric phenol. It is semi-solid and
Epoxy equivalent is 218, hydrolyzable chlorine is 0.07 w
It was t%.

Using this as a main ingredient, a cured molded product was produced in the same manner as in Example 1 (8). The results of the viscoelasticity measurement of this molded material are
As shown in the figure.

Although the elastic modulus is lower than that of Comparative Example 1, the glass transition temperature is also as low as 168°C, and it is inferior to Example 1 in terms of heat resistance. As described above, the polyphenol-J glycidyl ether obtained by the method of the present invention has excellent properties as a main ingredient for sealing.

[Brief explanation of the drawing]

FIG. 1 shows the viscoelasticity measurement results of the molded products of Example 1, Comparative Example 1, and Comparative Example 2 using solid lines, dotted lines, and dashed-dotted lines. Each line on the top shows the modulus of elasticity of the molded article, the numerical value of which is on the left vertical axis. Each lower line indicates tan δ, and the peak on the high temperature side corresponds to α dispersion. c7) The numerical value of tan δ is shown on the right vertical axis. The temperature at the peak point of α dispersion of tan δ was defined as the glass transition temperature.

Claims (1)

Scope of Claims: (1) (Li) The compound represented by the general formula θ~100 moJ%, the compound represented by the general formula 0-100 moJ%, and the compound represented by the general formula 0-80 mole% (However, the total of (I) to (4) is 100 mol%. In the formula, Rt - R6 is a hydrogen atom,
They are the same or different groups selected from 8 alkyl groups, aromatic groups and halogen atoms, and R8-R8 are selected from alkyl groups having 1 to 10 carbon atoms, aromatic groups, aryl groups and halogen atoms. They are the same or different groups. ) general formula % formula % () (where n is an integer from 2 to 12, m is 2n-2 or 2n, and X is a halogen atom). (41) Reacting the condensate and aldehydes in the presence of an acid catalyst to form a polyhydric phenol; (b) Reacting the polyhydric phenol and epihalohydrin; A method for producing glycidyl ether of polyhydric phenol, which comprises reaction and conversion to glycidyl ether. (2) The compound represented by general formula (I) is phenol, m-cresol, m-ethylphenol, m-isopropylphenol, 8-n-propylphenol, 3-n-propylphenol,
Chlorphenol, 8-bromophenol, 8,5-xylenol, 8,5-dichlorophenol, or 8-
Claim 1 which is chloro, 5-methylphenol
Manufacturing method described in section. (8) The compound represented by the general formula (It) is P-
Propenylphenol, 0-benzylphenol 6-
n-amyl-m-cresol, 0-cresol, P-
Cresol, 0-ethylphenol, P-ethylphenol, 0-phenylphenol, P-phenylphenol, P-1-pentylphenol, pt-butylphenol, O-chlorophenol, 4-chloro-8,5-
The manufacturing method according to claim 1, which is xylenol, 0-aryffrephenol or nonylphenol. (4) The compound represented by the general formula @) is 2-mo-butyl-4-methylphenol, 2,4-xylenol, 2
, 6-xylenol, 2,4-dichlorophenol, dichloroxylenol, dibromxylenol, 2,4.
The manufacturing method according to claim 1, which is 5-h dichlorophenol and 6-h dichlorophenol. (5) The production method according to claim 2, wherein the 10-genated hydrocarbon represented by general formula (V) is dichloroethane.