JPH0730060B2 - Method for producing monovalent or polyvalent phenol glycidyl ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for producing a glycidyl ether of a monohydric or polyhydric phenol, which is preferably used as an epoxy resin for the electric and electronic industries.

<Prior Art> In the glycidyl ether of monohydric or polyhydric phenol used as electric and electronic materials, it is essential that the content of hydrolyzable chlorine is low.

That is, the hydrolyzable chlorine has an adverse effect such as deterioration of electric insulation and corrosion of lead wires.

In particular, it is essential that the content of hydrolyzable chlorine is small in glycidyl ether of monohydric or polyhydric phenol as a raw material for encapsulating integrated circuits using semiconductors.

For example, in an integrated circuit with an integration degree of 64 kilobits or more, the content of hydrolyzable chlorine is required to be 600 ppm or less.

If the degree of integration is higher, it is required to be 300 ppm or less.

In addition to the low content of hydrolyzable chlorine, the lower epoxy equivalent is more desirable.

That is, when the epoxy equivalent is low, the crosslink density after curing is high, and as a result, the glass transition temperature (Tg) is high.

High glass transition temperature means high heat resistance,
This heat resistance is also a main physical property required of an epoxy resin as a semiconductor sealing material.

Various manufacturing methods have been investigated to reduce hydrolyzable chlorine.

For example, JP-B-52-46931 discloses that a chlorohydrin ether of a phenol is produced from a phenol and an excess of epichlorohydrin using a quaternary ammonium salt or a quaternary ammonium base as an addition catalyst, followed by anhydrous water. A method for producing a glycidyl ether of phenols by adding sodium oxide and dehydrochlorinating from a chlorohydrin ether group is described.

In JP-A-55-141479, a chlorohydrin ether of phenols is produced from phenols and epichlorohydrin using an addition catalyst such as quaternary ammonium salt, and excess epichlorohydrin is removed by distillation. Then, a method for producing glycidyl ether of phenols by dehydrochlorination with an aqueous solution of alkali metal hydroxide is described.

Further, JP-B-59-40831 describes a method for producing a glycidyl ether of a monohydric or polyhydric phenol using a quaternary ammonium salt or a quaternary ammonium base in the presence of a cyclic or linear ether compound. Has been done.

<Problems to be Solved by the Invention> An object of the present invention is to obtain a monohydric or polyhydric phenol glycidyl ether having a low epoxy equivalent and a low content of hydrolyzable chlorine.

Conventionally, when trying to reduce the content of hydrolyzable chlorine, there is almost no difference in the reactivity between the chlorine group and the epoxy group, and this is often accompanied by an increase in the epoxy equivalent.
In JP-40831, the content of hydrolyzable chlorine is reduced to about 280 ppm, but the epoxy equivalent is as high as 210.

On the other hand, in JP-B-52-46931 having a low epoxy equivalent, the hydrolyzable chlorine is as high as 1000 ppm, and in JP-A-55-141479, the hydrolyzable chlorine is 700 ppm or more and a sufficient improvement effect cannot be seen. .

The present invention provides a glycidyl ether of a monohydric or polyhydric phenol having a low epoxy equivalent and a low content of hydrolyzable chlorine, which is suitable for electronic materials.

<Means for Solving Problems> The present invention is a monohydric or polyhydric phenol and epichlorohydrin are reacted by adding an alkali metal hydroxide in the presence of a cyclic linear ether compound and onium salt, Alternatively, the present invention relates to a method for producing a glycidyl ether of a polyhydric phenol, wherein an anion having an ionic radius of 1.68Å or more is present in the method for producing a glycidyl ether of a polyhydric phenol.

The monohydric or polyhydric phenols used in the present invention are monohydric or polyhydric phenols consisting of a phenol unit substituted or unsubstituted with a halogen, an alkyl group, an allyl group, an alkenyl group, an aryl group or an aralkyl group. And specifically, phenol, orthocresol, metacresol, paracresol, diphenolmethane (bisphenol F), diphenolethane, diphenolpropane (bisphenol A), polyvinylphenol,
Polyisopropenylphenol, tetrabrominated bisphenol A, 1,1-bis- (4-hydroxyphenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1,1-dimethylmethane, phenol Novolak,
Brominated phenol novolac, cresol novolac,
Brominated cresol novolak, resorcin novolak,
Examples include, but are not limited to, brominated resorcinol novolac, resorcin, hydroquinone, methylresorcin, bisphenol A tetrachloride, and the like.

The amount of epichlorohydrin used in the present invention is preferably 2.5 to 20 mol, and more preferably 4 to 15 mol, per 1 mol of phenolic hydroxyl group.

If the amount of epichlorohydrin used is low, the formation of high molecular weight products by intermolecular reaction causes quality deterioration such as increase in melt viscosity of glycidyl ether of monohydric or polyhydric phenol, and further increases gel formation, which is industrially unfavorable. This is because it is profitable, and when the amount of epichlorohydrin used is large, the volume of the reaction mixture increases, which causes industrial disadvantages such as a decrease in productivity.

The alkali metal hydroxide used in the present invention is specifically sodium hydroxide, potassium hydroxide or the like.

The amount of the alkali metal hydroxide used is preferably about equimolar to 1 mol of the phenolic hydroxyl group.

When the amount of alkali metal hydroxide used is small, the amount of by-produced gel is small, which is advantageous in production, but hydrolyzable chlorine remains.

A large amount of the alkali metal hydroxide used increases the amount of gel, which is disadvantageous in manufacturing.

The cyclic or linear ether compound used in the present invention specifically includes, but is not limited to, dioxane, diethoxyethane, tetrahydrofuran, diethyl ether and the like.

The amount of these ether compounds used is preferably 10 to 100 parts by weight per 100 parts by weight of epichlorohydrin.

When the amount used is less than 10 parts by weight, the effect of the present invention is not so remarkable.

If the amount used is too large, the intermolecular reaction proceeds and the epoxy equivalent increases, which is not preferable.

Specific examples of the onium salt used in the present invention include terratramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and tetrabutyl. Quaternary ammonium salts such as ammonium iodide, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate trioctylmethylammonium chloride, choline chloride, benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide, Tetrabutylphosphonium chloride, tetrabutylphosphonium Examples include quaternary phosphonium salts such as romide, tetrabutylphosphonium iodide, tributylhexadecylphosphonium bromide, tributylmethylphosphonium iodide, and methyltriphenylphosphonium iodide, and tertiary sulfonium salts such as trimethylsulfonium iodide. It is not limited.

The amount of onium salt used is preferably 0.001 mol or more per 1 mol of the phenolic hydroxyl group.

If the amount used is less than 0.001 mol, the effect of reducing hydrolyzable chlorine is not sufficient.

The ionic radius referred to in the present invention is the numerical value in various documents,
Although there is a description of the measurement method, for example, Chemistry Handbook Basic Edition Revised 2nd Edition (June 20, 1975, published by Maruzen Co., Ltd.), page 1407 and Huey Inorganic Chemistry (above) (Translated by Koji Kodama, Hiroshi Nakazawa, No. 1)
First edition, October 25, 1984, issued by Tokyo Kagaku Doujin Co., Ltd.)
Described on pages 72 to 78, especially Tables 3.4 and 3.5
Numerical examples are shown in.

Ionic radius to be used in the present invention is not particularly limited as more anions 1.68Å but, Br from those commonly easily available ^{-, I -, S -,} SH -, CN -, ClO ₄ ^-, BF ₄ ^-
Inorganic ions, such as, CH ₃ -S ^-, There are organic ions such as.

Examples of substances that supply these anions include alkali metal salts and ammonium salts of the above ions. Specifically, sodium hydrosulfide, sodium sulfide, sodium methylthiolate, sodium phenylthiolate, sodium benzoate, potassium iodide, potassium cyanide. , Potassium thiocyanate, potassium perchlorate, sodium tetrafluoroborate, etc., but are not limited thereto.

The amount of anion having an ionic radius of 1.68 Å or more is preferably 0.005 to 2.0 g ion per mol of onium salt.

More preferably, it is 0.1 to 1.0 g ion.

When the amount used is small, the epoxy equivalent increases, and when the amount used is large, the effect of reducing the hydrolyzable chlorine becomes insufficient.

In the present invention, the epoxidation reaction of phenols can be carried out by a known method except that the specific compound as in the present invention is used. For example, it can be carried out as follows.

First, the monohydric or polyhydric phenol and epiclohydrin are mixed in the ratio described above.

Solid phenols are also dissolved in epichlorohydrin to form a uniform solution.

A cyclic or linear ether compound is further added to this and mixed.

The reaction is carried out by adding an onium salt and then an alkali metal hydroxide while stirring and mixing.

Since the addition of alkali metal hydroxide causes a uniform reaction,
It is added in small portions or continuously over 2 to 7 hours.

If it is put in temporarily, the reaction locally proceeds and gel is formed, which is not preferable.

This reaction is carried out under normal pressure or reduced pressure at a temperature of about 100 to 1 under normal pressure.
Under reduced pressure, the content liquid is azeotroped while being kept at about 50 ° C to 80 ° C under reduced pressure, depending on the pressure.

Volatile components are condensed, the condensate is separated into an organic layer and an aqueous layer, and the organic layer is dehydrated by returning it to the reaction system.

The anion having an ionic radius of 1.68Å or more may be added to the reaction system at any time before or after the start of the reaction.

After completion of the reaction, first, unreacted epichlorohydrin and cyclic or linear ether compounds are removed by distillation, and then dissolved in a ketone such as methyl isobutyl ketone or an aromatic hydrocarbon solvent such as toluene, and insoluble alkali metal The salt is removed separately or by washing with water, and the solvent is removed by distillation to obtain a monohydric or polyhydric phenol glycidyl ether.

The epochine equivalent in the present invention is defined by the number of grams of epoxy resin containing 1 gram equivalent of epoxy group.

Further, hydrolyzable chlorine is an epoxy resin dissolved in dioxane, and chloride ion desorbed when an alcohol solution of potassium hydroxide is added and heated under reflux for 30 minutes is quantified by titration with a silver nitrate solution, It is represented by the weight percentage of chlorine atoms.

Hereinafter, the present invention will be described in detail with reference to Examples, but the invention is not limited thereto.

<Examples 1 to 6 and Comparative Examples 1 to 4> Using a separable flask having a capacity of 1 and having a thermometer, a dropping funnel, a stirring blade, and a separation tube with a cooling tube, phenols were added under the conditions shown in Table 1. Glycidyl ethers of phenols were synthesized from epichlorohydrin.

Phenol, epichlorohydrin, and cyclic or linear ether compound were uniformly dissolved, and then an onium salt was added and dissolved.

At a temperature of about 80 ° C and a pressure of 250 mmHg, add an alkali metal aqueous solution to 4
Added continuously over time.

The substance supplying the anion was added in the amount and time shown in Table 1.

After completion of the reaction, unreacted epichlorohydrin cyclic or linear ether compound and trace amount of residual water were removed by distillation under reduced pressure.

The glycidyl ether of phenols containing the by-product salt obtained at this time was dissolved in methyl isobutyl ketone, hot water was further added to dissolve the by-product salt and the onium salt, and the organic layer and the aqueous layer were separated. Finally, the trace amount of water contained in methyl isobutyl ketone containing glycidyl ether of phenols was removed by distillation, the trace amount of remaining salt was separated, and then methyl isobutyl ketone was removed by vacuum distillation to obtain glycidyl ether of phenols. The hydrolyzable chlorine of the obtained glycidyl ether of phenols was measured. Table 1 shows the type of each component in each example, the charged amount, the number of moles, the reaction conditions, and the like. Table 2 shows the amounts of hydrolyzable chlorine and epoxy equivalent of the obtained glycidyl ethers of phenols.

<Effects of the Invention> According to the present invention, by using an anion having an ionic radius of 1.68Å or more and an onium salt in combination, the hydrolyzable chlorine content is as low as 300 ppm or less and the epoxy equivalent is less than 200, a monohydric or polyhydric phenol glycidyl. Ether is obtained.

This glycidyl ether is preferably used as an epoxy resin for sealing highly integrated circuits.

Claims (1)

[Claims] 1. A monohydric or polyhydric phenol and epichlorohydrin are reacted by adding an alkali metal hydroxide in the presence of a cyclic or linear ether compound and an onium salt to give a monohydric or polyhydric phenol glycidyl ether. A method for producing a glycidyl ether of a monohydric or polyhydric phenol, characterized in that an anion having an ionic radius of 1.68Å or more is present.