JPS59227874A - Preparation of glycidyl ether of polyhydric phenol - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by reacting a phenol with an unsaturated and an saturated hydrocarbon aldehyde in the presence of an acid catalyst to give a polyhydric phenol, treating it 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%) is reacted with an unsaturated hydrocarbon aldehyde shown by the formula IV (n is 2-6) and a saturated hydrocarbon aldehyde simultaneously or in this order in the presence of an acid catalyst to give a polyhydric phenol, which is reacted with an epihalohydrin, to give the desired substance. A weight ratio of the unsaturated aldehyde to the saturated aldehyde is (98/2)-(50/50). EFFECT:A small amount of impurity ions are produced, 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 can produce a cured product with a small amount of impurity ions and 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 a glass transition temperature that is 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 second 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 leprosy rate, it has been considered to add a flexibility imparting agent to the glycidyl ether of cresol novolak, but this lowers the glass transition temperature of the cured product. 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.

Glycidyl ethers of various polyhydric phenols have been developed as a method for obtaining a cured product with a low elastic modulus, but these also 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, in Japanese Patent Publication No. 51-41919, l.

It is described that glycidyl ether of polyhydric phenol obtained by the reaction of 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 the cured product containing glycidyl ether as the main ingredient for solid bisphenol is higher than the heat distortion temperature of the cured product containing glycidyl ether as the main ingredient of Talesol novolac, which is commonly used for sealing materials. It is also about 40°C lower. As described above, generally speaking, increasing the glass transition temperature and lowering the elastic modulus are contradictory physical properties required.

The present inventors have conducted extensive research on 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 inventors have discovered that this object can be achieved by using a specific condensing agent when doing so, leading to the present invention.

That is, the present invention provides (1) phenols consisting of 0 to 100 mol% of the compound represented by the general formula, 0 to 100 mol% of the compound represented by the general formula, and 0 to 80 mol% of the compound represented by the general formula (provided that The total of I) to (2) is 100 mol%.In the formula, R1 to R6 are hydrogen atoms, and have 1 to 8 carbon atoms.
are the same or different groups selected from alkyl groups, aromatic groups and halogen atoms, and R6-R8 have 1 carbon number.
~10 alkyl groups, aromatic groups, arylCnH2n
-t-CHO(N) (wherein n is an integer from 2 to 6)
Hydrocarbon aldehyde is added simultaneously or in this order to acid Pl! lI
This is a method for producing glycidyl ether of polyhydric phenol, which comprises reacting the polyhydric phenol with shrimp halohydrin to form a polyhydric phenol in the presence of a medium, and converting the polyhydric phenol into glycidyl ether. Specific examples of this theory include phenol, m-cresol, nl-ethylphenol, m-isopropylphenol, 3-n-propylphenol, 8-chlorophenol, 3-bromophenol, 8.5-xylenol, 8.5- Examples include dichlorophenol, 3-chloroJ5-methylphenol, but the scope of the present invention is not limited thereto.

Specific examples of the general formula of the present invention (represented by ITI; t = earthen wall) include p-propenylphenol, 0-, benzylphenol, (i-n-amyl-m-cresol, 0-cresol, p-cresol, 0-ethylphenol, P-phenylphenol, p-t-pentylphenol, p-t-fujithiphenol, 0-chlorophenol, 4-chloro-3,5-xylenol, 0-allylphenol, nonylphenol , 0-bromophenol, etc., but the scope of the present invention is not limited thereto.

Specific examples of the phenol represented by the general formula (2) of the present invention include 2-t-phthyl-4-methylphenol, 2.4-xylenol, 2.6-xylenol,
2.4 dichlorophenol, 2.4 dibromophenol, dichloroxylenol, dibromxylenol, 2.
Examples include 4.5-1 lychlorophenol and 6-phenyl-2-chlorophenol, but the scope of the present invention is not limited thereto.

The phenols of 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 (U), and 0 to 80 mol% of the compound represented by general formula (2). %. However, (1)
The total amount of (7) is 1l-100% by mole.

The phenol of the present invention is reacted with an unsaturated hydrocarbon aldehyde represented by the general formula Qv) and a saturated hydrocarbon aldehyde simultaneously or in this order in the presence of an acid catalyst to form a polyhydric phenol. 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 given in Encyclopedia of Polymer Science and Technology (Interscience Publications) No. 1.
As described in the section on phenolic resins on page 1 of Vol. acrolein metaacrolein,
These include crotonaldehyde and senecialdehyde, preferably acrolein, methacrolein, and crotonaldehyde, but the scope of the present invention is not limited thereto. Further, specific examples of the saturated hydrocarbon aldehyde 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, polyhydric phenols are dissolved in epihalohydrin, an alkali metal hydroxide bath solution is continuously added to this solution, water and epihalohydrin are distilled from the reaction mixture, and the distilled liquid is separated to form an aqueous layer. It can be produced using a production method in which shrimp halohydrin is removed and returned to the reaction system.

Incidentally, this reaction can also be carried out in the presence of a cyclic or linear ether. Examples of A-form 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 glycidyl ether of polyhydric phenol obtained by the method of the present invention, which includes phenol novolac, diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, Hardeners such as benzophenonetetracarboxylic anhydride, silica,
Inorganic fillers such as alumina, talc, clay, and glass fiber; hardening accelerators such as imidazoles, tertiary amines, and phenols; internal mold release agents such as stearic acid, calcium stearate, carba wax, and Monkun Sox; A composition containing a flame retardant imparting agent such as glycidyl ether of tetrabromobisphenol, if necessary, can be suitably used as a material for electrical and single-core industries, particularly as a sealing agent 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 should be added in an amount of about 0.2 to 2.
0% by weight is used in each case.

The novel glycidyl ether of polyhydric phenol of the present invention can provide a cured product with a lower elastic modulus than the conventional glycidyl ether of orthocresol novolac or glycidyl ether of phenol novolak, and can prevent a decrease in the glass transition temperature. , and the hydrolyzable chlorine content is small.

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 30 minutes, which is determined by back titration using a silver nitrate bath solution. It is defined by the M amount n fraction of chlorine atoms in the compound.

Example 1 (1) Synthesis of polyhydric phenol It equipped with a thermometer, cooling tube, dropping funnel, and stirrer
Add 1 part of orthocresol to the flask, OE:) Ii and Mt
0.01 mol of para-toluenesulfonic acid was added as J5 and thoroughly mixed. 0.25 mol of acrolein was added dropwise over about 1 hour while maintaining the system temperature at 40 to 60°C, kept warm for 1 hour, and then gradually raised to 90 to 60°C.
Set to 100"C! Next, formalin water bath fi0.05
mol (as formaldehyde) dropwise in about 1 hour,
It was kept warm for 2 hours. Then, the catalyst acid was neutralized with sodium hydroxide, and the aqueous phase was separated. After further washing with water, the remaining water was removed by distillation by heating, and then the temperature was increased to 150° under reduced pressure.
The volatiles were removed by heating to 20°C. The condensate obtained at this time was a reddish-brown polyhydric phenol that was solid at room temperature.

(branch)) Synthesis of glycidyl ether of polyhydric phenol 12 equipped with a thermometer, separation tube, dropping funnel, and stirrer
In a flask, add 1.0 mol of the polyhydric phenol obtained in (1) (as phenolic water a group) to 7 mol of epichlorohydrin,
Dissolves in 0 mol.

The temperature was maintained at 64° C., the pressure was 150 tmHIl, and a 48% NaOH aqueous solution was continuously added over 6 hours.

During this time, 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 69°C. Softening point is JIS-[2
851 (petroleum asphalt softening point test method (ring and ball method)). The epoxy equivalent weight was 197 and the hydrolyzable chlorine was 0.06 wt%. The average number of phenyl nuclei calculated from the GFC curve was 5.8.

(3) Viscoelasticity measurement of cured product 1.0 mol of glycidyl ether of polyhydric phenol obtained in (2) (epoxy group, specifically 206f
), 1.0 mol of phenol novolak (as a phenolic hydroxyl group), and 0.8 parts by weight of tris ÷ dimethylaminomethyl ÷ phenol (manufactured by Sumitomo Chemical Co., Ltd., SUMIKI, Ar■D) based on the total amount as a curing accelerator. A composition was prepared by roll kneading. Next, this composition was molded into a 1-inch sheet by pressurizing and heating. This molded product was post-cured at 170° C. for 5 hours to produce a cured molded product. This molded product has a glass transition temperature of 213°C and an elastic modulus at 150"C of 1.5 x 10" dyne/cr/1, and in the case of the glycidyl ether of Comparative Example 1, it is 2.5 x 10
Since it is dyne/cd, the elastic modulus is about half.

Comparative Example 1 Commercially available glycidyl ether of cresol novolak (manufactured by Sumitomo Chemical Co., Ltd., Sumiepoxy E8cN-22
A cured molded product was prepared in the same manner as in Example 1 (3) using 0) as the main ingredient.

An elastic modulus lower than that of this cured molded product is desired in the market as a sealant for S-product circuits, and the glycidyl ether of polyhydric phenol of Example 11 satisfies this requirement. Furthermore, the glass transition temperature of the molded product of Comparative Example 1 was 208°.
It was C.

Claims (1)

Scope of Claims: (1) (li) Phenols consisting of 0 to 100 mol% of the compound represented by the general formula, 0 to 100 mol% of the compound represented by the general formula, and 0 to 80 mol% of the compound represented by the general formula (However, the total of (I) to @) shall be 100 mol%.In the formula, R1-R6 are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aromatic groups, and halogen atoms. They are the same or different groups, and R6-R8 have 1 to 1 carbon atoms.
They are the same or different groups selected from 10 alkyl groups, aromatic groups, aryl groups, and halogen atoms. ) (=) general formula % formula % () (in the formula, n is an integer of 2 to 6) An unsaturated hydrocarbon aldehyde and a saturated hydrocarbon aldehyde are reacted simultaneously or in this order in the presence of an acid catalyst. (i) A method for producing a glycidyl ether of a polyhydric phenol, which comprises: (i) reacting the polyhydric phenol with an epihalohitrint to form a glycidyl ether. (Support) The compound represented by the general formula (1) is phenol, In-cresol, m-ethylpheno-J, m
-isopropylphenol, 3-n-propylphenol, 8-chlorophenol, 8-bromophenol, 3
．． 5-xylenol, 3,5-dichlorophenol, or 3-chloro J5 methylphenol, the manufacturing method according to claim 1. (3) The compound represented by the general formula (Ill) is P-propenylphenol, 0-benzylphenol-J, 6-n
-amyl-m-cresol, 0-cresol, p-cresol, 0-ethylphenol, P-ethylphenol, O-phenylphenol, p-phenylphenol,
pt-pentylphenol, pt-butylphenol, O-chlorophenol, 4-chloro range 1. The production method according to item 1. (4) The compound represented by general formula (2) is 2-t
-Butyl-4-methylphenol, 2,4-xylenol, 2,6-xylenol, 2,4-dichlorophenol, and dichloroxylenol phenol. (5) The manufacturing method according to claim 1, wherein the compound represented by the general formula (to) is acrolein or methacrolein. (6) Formula (the ratio of unsaturated hydrocarbon aldehyde and saturated hydrocarbon aldehyde represented by chrysanthemum is 98/2 to 501
50 (weight ratio).