JP2001316388A - Method for reducing residual organic solvent in crystal of tris-(2,3-epoxypropyl)-isocyanurate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for extremely reducing the residual organic solvent of crystal of tris-(2,3-epoxypropyl)-isocyanurate, especially β type tris-(2,3- epoxypropyl)-isocyanurate obtained by a recrystallization method. SOLUTION: This method for reducing a residual organic solvent in crystal of tris-(2,3-epoxypropyl)-isocyanurate comprises grinding particles of crystal of tris-(2,3-epoxypropyl)-isocyanurate obtained by a recrystallization method while evaporation of volatile components from the surface of the particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to tris- (2,3-
(Epoxypropyl) -isocyanurate A method for reducing the residual organic solvent in a crystal by removing the solvent remaining in the crystal from the particle surface by evaporation of volatile components from the particle surface, particularly by mechanical pulverization in an air stream. It is.

[0002]

2. Description of the Related Art Solder resist inks using a photosensitive prepolymer and a thermosetting resin in combination with a recent demand for characteristics of a solder resist material such as adhesion, electric insulation, solder heat resistance, and solvent resistance have been increasing. The composition has been used. That is, after the solder resist pattern is formed by the photosensitive prepolymer, the above-mentioned required characteristics are to be satisfied by thermosetting. In addition, the demand for higher density of printed wiring boards with the recent reduction in the size and weight of electronic devices, lower bleeding when forming solder resist patterns for surface mounting of components, and more precise embedding between circuits is increasing. ing. Therefore, as a thermosetting resin used in combination with the solder resist ink, a fine solid epoxy having high solvent resistance is desired.

[0003] Tris- (2,3-epoxypropyl) -isocyanurate is an example of a solid epoxy satisfying the above-mentioned required properties. Tris- (2,3-epoxypropyl) -isocyanurate has three asymmetric carbons, and all three asymmetric carbons are aligned (2R, 2 ′).
R, 2 "R) -tris- (2,3-epoxypropyl)
Crystals that are equimolar mixtures of -isocyanurate and (2S, 2'S, 2 "S) -tris- (2,3-epoxypropyl) -isocyanurate are generally referred to as β-type crystals and have a temperature of about 150 ° C. It is known that a high melting point type crystal is provided, because the two types of enantiomers form a molecular lattice having a pair of strong six hydrogen bonds and form a crystal lattice. On the other hand, one of the three asymmetric carbons
(2R, 2R, 2S) -tris- (2,3-epoxypropyl) -isocyanurate and (2S, 2S, 2R) -tris- (2,3-epoxypropyl) -isocyanate having two different optical anisotropies Crystals composed of a mixture of nurate are generally referred to as α-type crystals and do not have the above-mentioned crystal structure, and thus give only a low melting point of about 100 ° C. The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal has not only a high melting point but also a very low solubility in various solvents, so that it can be used as a cross-linking agent for heterogeneous compounds and reactive polymers. When used as a reactive mixture of a mold, the reaction during storage until forcibly cured does not proceed. Until now, it has been used for electric and electronic material applications, for example, a photo-curing / thermo-setting solder resist ink composition.

The liquid epoxy composition may be thickened during storage due to the dissolution of a part of the epoxy compound in a solvent, or may cause poor elution when washing away the unexposed portion due to sticking with the photosensitive prepolymer. . 7-177
No. 37, β-type tris- (2,3-epoxypropyl)
Using isocyanurate as the poorly soluble epoxy compound; Β-type tris- (2,3
The (epoxypropyl) -isocyanurate fine particles are in a state of being wrapped in the photosensitive prepolymer, and do not lower the solubility of the unexposed portion of the photosensitive prepolymer.
Further, since it is hardly soluble in an organic solvent, the exposed portion is hardly affected by the developing solution, and does not cause a decrease in sensitivity. Furthermore, the storage stability of the solder resist ink composition is excellent.

Conventionally, β-type tris- (2,3-epoxypropyl) -isocyanurate has been
(2,3-epoxypropyl) -isocyanurate and α
As a method for dividing and producing tris- (2,3-epoxypropyl) -isocyanurate, α-tris-
(2,3-Epoxypropyl) -isocyanurate dissolves relatively well and β-type tris- (2,3-epoxypropyl) -isocyanurate is difficult to dissolve, for example, a resolution method using an alcohol such as methanol. was there. For example, the Journal of Thermal Analysis (Journal of Thermal Analysis)
is) Vol. 36 (1990), p. 1819, the separation is carried out using a methanol solvent. Plus
Und Kautestuk (Plaste und Ka)
utschuk) 23 Jahrgang Heft4 /
In 1975, first, β-type tris- (2,3-epoxypropyl) -isocyanurate was separated using a methanol solvent, and then β-type tris- (2,3-epoxypropyl) -isocyanurate was purified with chloroform. ing. In addition, Vol. 3 (1990)
On page 169, tris- (2,3-epoxypropyl) -isocyanurate obtained by synthesis is put into methanol, heated and stirred, and undissolved components are filtered off. The obtained undissolved product is methyl ethyl ketone. Recrystallize and form β-tris
(2,3-Epoxypropyl) -isocyanurate crystals are obtained.

[0006] Most of the β-type tris- (2,3-epoxypropyl) -isocyanurate obtained by such a dividing method is difficult to grow crystals and has a small particle diameter, so that the filtering operation becomes extremely difficult in the filtration step. I do. Therefore, it is not preferable that the crystals obtained by recrystallization are too fine.

In one division operation of the above division method, β-type tris- (2,3-epoxypropyl)-
Recrystallization solvent and chlorine-containing impurities in isocyanurate crystals,
Since other impurities are likely to be included, it is necessary to remove the crystal by further recrystallization or melting the crystal once. In particular, when the residual organic solvent is not sufficiently removed, when used for a solder resist material or the like, pores in which the solvent evaporates are formed on the surface of the printed wiring board, and the original characteristics of the resist material cannot be sufficiently exhibited. Further, a problem may occur in an application requiring surface smoothness. Further, when the residual organic solvent is a halogenated hydrocarbon, it is not preferable for use in electronic materials.
Further, when the residual organic solvent is a protic organic solvent, the storage stability of the composition may be impaired by protons.

In Japanese Patent Publication No. 48-24039, a chlorhydrin ester of isocyanuric acid obtained by reacting cyanuric acid with epichlorohydrin is subjected to dehydrochlorination with an alkali to separate an alkali metal chloride produced. The solution of (2,3-epoxypropyl) -isocyanurate in epichlorohydrin is concentrated to give tris- (2,3-
Epoxypropyl) -isocyanurate concentration 50-60
%, Cooled to 20 to 25 ° C., and tris- (2,3-epoxypropyl)-with a yield of 27% based on cyanuric acid.
Crystals of isocyanurate are obtained. However, since it is crystallized from an epichlorohydrin solution, there is a problem that epichlorohydrin and the like are contained in a large amount in the crystal. Furthermore, epichlorohydrin is not only harmful to the human body, but is also composed of hydrolyzable chlorine harmful to electronic materials, so that it is desirable to minimize the amount. However, in order to remove epichlorohydrin in the crystal, it is impossible to remove the residual epichlorohydrin unless the crystal is heated to a temperature equal to or higher than the melting point and once melted, and such a method makes the production process more complicated. , Production costs are high and it is not industrial.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by a recrystallization method, particularly a β-form tris- (2,3-epoxypropyl) -isocyanate. It is an object of the present invention to provide a method for extremely reducing the residual organic solvent of a nurate crystal.

[0010]

According to the present invention, as a first aspect, tris- (2,3-epoxypropyl) -isocyanurate crystalline particles obtained by a recrystallization method are used as a raw material, and volatile components are removed from the surface of the particles. By grinding under the evaporation of
Method for reducing residual organic solvent in tris- (2,3-epoxypropyl) -isocyanurate crystals, as a second aspect, starting material tris- (2,3-epoxypropyl)-
The isocyanurate crystal particles are reacted with cyanuric acid and epichlorohydrin in the presence of a catalyst to obtain a chlorohydrin ester of isocyanuric acid. Tris- (2,3-epoxypropyl) -isocyanurate obtained by removing a solvent from a reaction solution containing (2,3-epoxypropyl) -isocyanurate is recrystallized using a solvent. The method for reducing a residual organic solvent according to the first aspect, and as a third aspect, the recrystallization solvent is acetonitrile, dichloroethane, dioxane,
The method for reducing a residual organic solvent according to the first aspect or the second aspect, which is toluene, dimethylformamide, methanol, ethanol, or isopropyl alcohol. As a fourth aspect, pulverization in which volatile components evaporate from the particle surface is performed in an air stream. The method for reducing a residual organic solvent according to any one of the first aspect to the third aspect, which is a pulverization performed in a fifth aspect, wherein the crystal grains are pulverized to an average particle diameter of 0.5 to 20 μm. The method for reducing a residual organic solvent according to any one of the first to fourth aspects, and as a sixth aspect, the method according to any one of the first to fifth aspects, in which the concentration of the residual organic solvent is 300 ppm or less. Method for reducing the residual organic solvent described,
As a seventh aspect, the tris- (2,3-epoxypropyl) -isocyanurate crystal particles have a β-type tris-
(2,3-Epoxypropyl) -isocyanurate crystalline particles, the method for reducing residual organic solvent according to any one of the first to sixth aspects, as an eighth aspect, acetonitrile, The method for reducing a residual organic solvent according to the seventh aspect, which is dichloroethane, dioxane, toluene, or dimethylformamide, and as a ninth aspect, any one of the first to eighth aspects, wherein the residual organic solvent is epichlorohydrin and acetonitrile. It is a method for reducing a residual organic solvent according to one of the aspects.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pulverization in which volatile components evaporate from the particle surface includes pulverization performed in an air stream and pulverization performed under reduced pressure. In particular, pulverization performed in an air stream is effective. Here, the air flow is a gas flow of air, an inert gas such as a nitrogen gas, an argon gas, or the like, and a nitrogen gas is particularly preferable.

The pulverization in the air stream is performed, for example, by a 200 AFG type counter jet mill manufactured by ALPINE, K Krimoto manufactured by Kurimoto.
This is performed using a pulverizer such as a J-200 type cross jet mill. This type of pulverizer is a mechanism in which high-pressure air or an inert gas (for example, nitrogen) is blown into a pulverizer together with a sample to collide and pulverize sample particles. The pressure of this gas is 1 to 10 kg / cm ² . With this gas flow rate, the volatile components evaporate from the surface of the particles newly generated by the pulverization, and the organic solvent contained in the crystals is reduced.
The process is performed until the crystal particles are pulverized to an average particle size of 0.5 to 20 μm. At this time, the concentration of the residual organic solvent in the pulverized crystalline particles is 300 ppm or less, usually 100 to 2 ppm.
Obtained at 00 ppm.

In the present invention, the tris- (2,3-epoxypropyl) -isocyanurate crystal particles have an average particle size of any tris- (2,3-epoxypropyl) -isocyanurate crystalline particles having an average particle diameter of more than 20 μm and 500 μm or less.
(2,3-Epoxypropyl) -isocyanurate crystals can also be used in the present invention. In particular, use of tris- (2,3-epoxypropyl) -isocyanurate crystals obtained by a recrystallization method. Is preferred.

That is, (a) 1 mol of cyanuric acid, (b)
5 to 180 mol of epichlorohydrin, and (c) at least one selected from the group consisting of a tertiary amine, a quaternary ammonium salt, a quaternary ammonium base, a trisubstituted phosphine, and a quaternary phosphonium salt as a catalyst. 3 to 6 mol of an alkali metal hydroxide or an alkali metal alcoholate is added to a reaction solution obtained by reacting 0.001 to 0.1 mol of the compound of interest, and after dehydrochlorination, the alkali metal salt is removed and tris is added. After obtaining a reaction solution containing-(2,3-epoxypropyl) -isocyanurate, the solvent is removed to obtain tris- (2,3-epoxypropyl) -isocyanurate.

In the method for producing the tris- (2,3-epoxypropyl) -isocyanurate crystal,
(C) Examples of the catalyst include tertiary amines such as tripropylamine, tributylamine, and N, N'-dimethylpiperazine. Examples of the quaternary ammonium salt include tetramethylammonium halide, tetraethylammonium halide, and tetrabutylammonium halide, and examples of the halide include chloride, bromide, and iodide. Examples of the quaternary ammonium base include tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide. Examples of the tri-substituted phosphine include tripropyl phosphine, tributyl phosphine, triphenyl phosphine, tolyl phosphine, and the like. Examples of the quaternary phosphonium salt include tetramethylphosphonium halide, tetrabutylphosphonium halide, and methyltriphenyl. Phosphonium halide, ethyltriphenylphosphonium halide and the like, and as the halide, chloride, bromide,
Iodide and the like. Among the compounds mentioned here, quaternary ammonium salts and quaternary phosphonium salts are preferred because the reaction proceeds less efficiently under milder conditions and the reaction proceeds efficiently. Particularly preferred are quaternary ammonium salts. Among them, tetramethylammonium halide, tetraethylammonium halide and tetrabutylammonium halide are used, and chloride and bromide are used as halides, whereby side reactions are further suppressed, and removal of the catalyst after the reaction is eliminated. Is also preferable because it can be easily removed by washing with water.

An alkali metal hydroxide or an alkali metal alcoholate is added to the reaction solution obtained as described above.
After adding about 6 mol and dehydrochlorinating, the alkali metal salt is separated by washing or filtration to obtain a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate. Examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of the alkali metal alcoholate include sodium methylate, sodium ethylate, potassium methylate, and potassium ethylate. . The tris- (2,3-epoxypropyl) -isocyanurate thus formed has β-tris- (2,3-epoxypropyl).
-Isocyanurate and α-type tris- (2,3-epoxypropyl) -isocyanurate in a weight ratio of 1: 3.

The thus obtained tris- (2,3-epoxypropyl) -isocyanurate is converted to acetonitrile,
Tris- (2,3-epoxypropyl) -isocyanurate recrystallized from dichloroethane, dioxane, toluene, dimethylformamide, methanol, ethanol, or isopropyl alcohol as a recrystallization solvent can be used as a raw material of the present invention. .

In the present invention, tris- (2,3-epoxypropyl) -isocyanurate containing the above-mentioned β-form and α-form can be used as a raw material.
(2,3-Epoxypropyl) -isocyanurate crystal particles can be preferably used.

The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal is, for example, a chlorohydrin ester of isocyanuric acid obtained by reacting cyanuric acid with epichlorohydrin in the presence of a catalyst. The alkali metal chloride produced by dehydrochlorination with an alkali is separated, and the solvent is evaporated from the resulting reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate. (3-epoxypropyl) -isocyanurate can be produced by recrystallization. At this time, as the recrystallization solvent, acetonitrile, dichloroethane, toluene, dioxane, dimethylformamide and the like can be used, and acetonitrile is particularly preferable.

Recrystallization is achieved by heating to a temperature at which tris- (2,3-epoxypropyl) -isocyanurate dissolves in the above-mentioned solvent and gradually cooling it. The cooling can be carried out slowly as it is, but it can also be carried out by adding a seed crystal. As this seed crystal, either β-form or α-form tris- (2,3-epoxypropyl) -isocyanurate can be used.

Tris- (2,3-
Epoxypropyl) -isocyanurate is filtered by suction,
It is separated by a filter press method, a centrifugal filtration method or the like.

Tris- (2,3) containing the liquid content filtered off
-Epoxypropyl) -isocyanurate can be washed with various organic solvents because it contains impurities as a component of the liquid content. Examples of the organic solvent include methanol,
Examples include ethanol, isopropyl alcohol, methyl ethyl ketone, acetonitrile, dimethylformamide, and epichlorohydrin.

In the present invention, the residual organic solvent to be reduced is
Epichlorohydrin, a reaction substrate, and a solvent used for recrystallization.

Β-tris obtained by recrystallization
The (2,3-epoxypropyl) -isocyanurate crystal has an average particle diameter of 10 to 500 μm. Among these particle diameters, the invention of the present application has an average particle diameter exceeding 20 μm and exceeding 5 μm.
Those having a range of not more than 00 μm can be used.

The β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by such a recrystallization method may be dried at room temperature to 90 ° C. under reduced pressure to obtain a residual organic compound inside the crystal. Solvent hardly decreases, usually 1000-2000
ppm, which causes a reduction in the purity of the product, and also causes a problem in use. In this case, the pressure is 100
By drying at a temperature of from 140 to 140C, preferably from 120 to 140C, the residual organic solvent can be reduced to 300 ppm or less. The above-mentioned temperature of 100 to 140 ° C., preferably 120 to 140 ° C. is the α-type tris- (2,3
-Epoxypropyl) -isocyanurate and at a temperature below the melting point of β-tris- (2,3-epoxypropyl) -isocyanurate. By drying in an air stream at this temperature, α-type tris
The β-type tris- (2,3-epoxypropyl) -isocyanurate crystal containing (2,3-epoxypropyl) -isocyanurate inside the crystal is an α-type tris-
The (2,3-epoxypropyl) -isocyanurate portion melts and becomes liquid. Through this liquid portion, the epichlorohydrin impurity and the organic solvent used for recrystallization are discharged from the crystal to the outside of the crystal.

However, according to the present invention, the obtained β-form tris- (2,3-epoxypropyl) -isocyanurate crystal is not less than the melting point of α-form tris- (2,3-epoxypropyl) -isocyanurate. The organic solvent remaining in the crystal can be reduced by performing the pulverizing step in an air stream at room temperature without passing through a drying step at 140 to 140 ° C, preferably 120 to 140 ° C.

The pulverization is performed by pulverizing the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal to an average particle diameter of 0.5 to 20 μm. This pulverization can reduce the residual organic solvent to 300 ppm or less.

The average particle size and the particle size distribution of the pulverized product are controlled by the pulverizing conditions and the classifying rotor.
When the (2,3-epoxypropyl) -isocyanurate crystal is pulverized to an average particle diameter of 0.5 to 20 μm, the organic solvent inside the crystal can be efficiently removed. The smaller the average particle size of the pulverized crystals, the higher the solvent removal rate. However, if the average particle size is too small, the pulverization efficiency will decrease. When the average particle size is 20 μm or more, the solvent removal rate is low.

Air or an inert gas is used for the air flow during the pulverization, and the volume specific resistance value of 2 × 10 ¹³ Ω · such as tris- (2,3-epoxypropyl) -isocyanurate is used.
When crushing organic substances as high as cm, an inert gas such as nitrogen gas is preferred to avoid the danger of dust explosion.

The preferable air flow rate for the sample supply amount depends on the shape of the apparatus and the air flow pressure.
Nitrogen pressure 6 kg / cm ² with FG type counter jet mill
When pulverizing with 5 to 40 Nm of nitrogen per 1 kg of sample
³ is preferable, and if it is less, the effect of removing the solvent decreases, and if it is more than that, the removing effect is not so large for the amount of nitrogen used.However, as the amount of nitrogen is large, the solvent is easily removed, and the dust concentration is generally low. There is an advantage that the risk of dust explosion is reduced due to the reduction.

In such a pulverizing method using an enormous amount of nitrogen, a method of collecting and reusing the used nitrogen gas stream is generally used in order to save the cost of nitrogen.
However, when the recovery and reuse of the nitrogen gas stream are performed continuously for a long period of time, the vapor concentration of the organic solvent in the nitrogen gas stream gradually increases, and thus the evaporation of the organic solvent from the particle surface is hindered. When the organic solvent has a high boiling point, it is possible to trap the solvent by cooling the recovered gas.However, an effective method is to always discharge a nitrogen gas stream at a constant discharge rate, By replenishing the gas, accumulation of the solvent vapor concentration in the gas stream can be prevented. The discharge amount of nitrogen gas is preferably about 2 to 20% by volume of the total nitrogen gas introduced per unit sample, that is, 0.1 to 8 Nm ³ per kg of sample.

<Method for Quantifying Organic Solvent Remaining in Crystal> The organic solvent remaining in the crystal is obtained by adding a 20-fold amount of an organic solvent other than for the purpose of quantification, such as dimethylformamide or acetonitrile, to the sample (crystal). At 80.degree. C., and can be quantified by gas chromatography.

[0033]

EXAMPLES (Production example of β-form tris- (2,3-epoxypropyl) -isocyanurate crystal by recrystallization method 1) Stirrer, thermometer, continuous dropping device, and epichlorohydrin and water under reduced pressure In a flask equipped with a device for concentrating boiling steam and returning only epichlorohydrin to the reaction system, 774 g (6 mol) of cyanuric acid and epichlorohydrin 8 were added.
328 g (90 mol) and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight were added, and 89
The reaction was carried out by refluxing while stirring at ~ 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 1 wt.
g under a reduced pressure of 100 to 60 Torr while maintaining
After reacting for an hour, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then washed with 4800 g of water.

Next, Tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method for recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate as acetonitrile as a recrystallization solvent will be described.

To a flask equipped with a stirrer and a thermometer were added 1000 g of tris- (2,3-epoxypropyl) -isocyanurate and 1000 g of acetonitrile, which were dissolved at 57 ° C. with stirring, and then heated to 50 ° C. After cooling, 7 g of β-form tris- (2,3-epoxypropyl) -isocyanurate is added as a seed crystal. Then, after cooling to 14 ° C. over 4 hours, the mixture was filtered by suction, and then cooled to 30 ° C.
The cake was washed with 0 g of methanol. The obtained cake was dried at 80 ° C. under reduced pressure for 4 hours. After drying, a β-type tris- (2,3-β) containing a melting point of 150 to 156 ° C., an epoxy equivalent of 101 g / eq, a hydrolyzable chlorine of 150 ppm, an average particle size of 75 μm, and 50 ppm of epichlorohydrin and 1360 ppm of acetonitrile remaining inside the crystal.
Epoxypropyl) -isocyanurate crystal 182 g
was gotten.

(Β-type tris- (2,3-
Production Example 2 of Epoxypropyl) -Isocyanurate Crystal 2) A flask equipped with a stirrer, a thermometer, a continuous dropping device, and a device for concentrating azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system. , Cyanuric acid 774 g (6 mol), epichlorohydrin 8
328 g (90 mol) and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight were added, and 89
The reaction was carried out by refluxing while stirring at ~ 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 1 wt.
g under a reduced pressure of 100 to 60 Torr while maintaining
After reacting for an hour, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then washed with 4800 g of water.

Then, tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method of recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate with toluene as a recrystallization solvent will be described.

In a flask equipped with a stirrer and a thermometer, 1000 g of the obtained tris- (2,3-epoxypropyl) -isocyanurate and 4000 g of toluene were added, and the mixture was dissolved at 110 ° C. with stirring. 65 ° C
After cooling, the cake was washed with 300 g of methanol. The cake obtained is reduced pressure
Dried at 80 ° C. for 4 hours. After drying, melting point 150-1
55 ° C., epoxy equivalent 102 g / eq, hydrolyzable chlorine 260 ppm, average particle diameter 45 μm, epichlorohydrin 50 ppm remaining inside the crystal, and toluene 1520 pp
Thus, 188 g of β-form tris- (2,3-epoxypropyl) -isocyanurate crystals containing m were obtained.

(Β-type tris- (2,3-
Production Example of Epoxypropyl) -Isocyanurate Crystalline 3) A flask equipped with a stirrer, thermometer, continuous dropping device, and a device equipped with a device for concentrating azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system. , Cyanuric acid 774 g (6 mol), epichlorohydrin 8
328 g (90 mol) and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight were added, and 89
The reaction was carried out by refluxing while stirring at ~ 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 1 wt.
g under a reduced pressure of 100 to 60 Torr while maintaining
After reacting for an hour, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then washed with 4800 g of water.

Next, Tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method for recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate using dioxane as a recrystallization solvent will be described.

1000 g of tris- (2,3-epoxypropyl) -isocyanurate and 1000 g of dioxane were added to a flask equipped with a stirrer and a thermometer, and dissolved at 75 ° C. with stirring. Cool down,
Β-type tris- (2,3-epoxypropyl) as seed crystal
7 g of isocyanurate are added. Next 3 over 4 hours
After cooling to 0 ° C., the mixture was filtered by suction, and the cake was subsequently washed with 300 g of methanol. The obtained cake was dried at 80 ° C. under reduced pressure for 4 hours. After drying, melting point 150
１５155 ° C., epoxy equivalent 101 g / eq, hydrolyzable chlorine 250 ppm, average particle diameter 60 μm, epichlorohydrin 50 ppm remaining inside the crystal and dioxane 146
185 g of β-form tris- (2,3-epoxypropyl) -isocyanurate crystals containing 0 ppm were obtained.

(Β-type tris- (2,3-
Production Example of Epoxypropyl) -Isocyanurate Crystalline 4) A flask equipped with a stirrer, a thermometer, a continuous dropping device, and a device equipped with a device for concentrating azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system. , Cyanuric acid 774 g (6 mol), epichlorohydrin 8
328 g (90 mol) and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight were added, and 89
The reaction was carried out by refluxing while stirring at ~ 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 1 wt.
g under a reduced pressure of 100 to 60 Torr while maintaining
After reacting for an hour, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then washed with 4800 g of water.

Next, tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method for recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate using dimethylformamide as a recrystallization solvent will be described.

1000 g of tris- (2,3-epoxypropyl) -isocyanurate and 1000 g of dimethylformamide obtained in a flask equipped with a stirrer and a thermometer
After dissolving at 65 ° C. with stirring, the mixture is cooled to 55 ° C., and 5 g of β-tris- (2,3-epoxypropyl) -isocyanurate is added as a seed crystal. Next, after cooling to 20 ° C. over 4 hours, the mixture was filtered by suction, and the cake was washed with 300 g of methanol. The obtained cake was dried at 80 ° C. under reduced pressure for 4 hours. After drying,
Melting point 150-154 ° C, epoxy equivalent 101 g / eq,
Β-type tris containing 200 ppm of hydrolyzable chlorine, 50 μm in average particle size, 50 ppm of epichlorohydrin remaining in the crystal and 1800 ppm of dimethylformamide
162 g of (2,3-epoxypropyl) -isocyanurate crystals were obtained.

(Β-type tris- (2,3-
Production Example of Epoxypropyl) -Isocyanurate Crystal 5) In a flask equipped with a stirrer, a thermometer, a continuous dropping device, and a device for concentrating azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system. ,
774 g (6 moles) of cyanuric acid, 8328 g (90 moles) of epichlorohydrin, and 213 g of a 15.5% by weight aqueous solution of tetramethylammonium chloride were added to the mixture to give 8
The reaction was carried out by refluxing while stirring at 9 to 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 50% by weight aqueous sodium hydroxide solution 153 was stirred.
While maintaining 6 g at 50 ° C., under a reduced pressure of 100 to 60 Torr,
After reacting for 6 hours, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then 4800g
And washed with water.

Then, tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method for recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate and 1,2-dichloroethane as a recrystallization solvent will be described.

1000 g of tris- (2,3-epoxypropyl) -isocyanurate obtained in a flask equipped with a stirrer and a thermometer, and 1,2 dichloroethane 1500
g, and dissolved at 73 ° C. with stirring, then cooled to 25 ° C. over 6 hours, filtered by suction, and
The cake was washed with 00 g of methanol. The obtained cake was dried at 80 ° C. under reduced pressure for 4 hours. After drying, a β-type tris containing a melting point of 150 to 154 ° C., an epoxy equivalent of 101 g / eq, a hydrolyzable chlorine of 220 ppm, an average particle diameter of 50 μm, and 50 ppm of epichlorohydrin remaining in the crystal and 1400 ppm of 1,2 dichloroethane.
165 g of (2,3-epoxypropyl) -isocyanurate crystals were obtained.

(Production Example of Tris- (2,3-epoxypropyl) -isocyanurate Crystal by Recrystallization Method)
6) A flask equipped with a stirrer, a thermometer, a continuous dropping device, and a device for concentrating azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system, 774 g (6 mol) of cyanuric acid, epichlorohydrin 8
328 g (90 mol) and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight were added, and 89
The reaction was carried out by refluxing while stirring at ~ 120 ° C for 5 hours. Next, the temperature of the reaction system was cooled to 50 ° C., and a 1 wt.
g under a reduced pressure of 100 to 60 Torr while maintaining
After reacting for an hour, dehydrochlorination was performed. Thereafter, the generated sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed with 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate, whereby an excess amount of sodium hydroxide was used. And then washed with 4800 g of water.

Next, tris- (2,2) obtained by washing with water was used.
The epichlorohydrin in the solution of 3-epoxypropyl) -isocyanurate was distilled off to obtain 1604 g of tris- (2,3-epoxypropyl) -isocyanurate having an epoxy equivalent of 105 g / eq. A method of recrystallization using this tris- (2,3-epoxypropyl) -isocyanurate with methanol as a recrystallization solvent will be described.

1000 g of the obtained tris- (2,3-epoxypropyl) -isocyanurate and 4000 g of methanol were added to a flask equipped with a stirrer and a thermometer, and the mixture was dissolved at 60 ° C. with stirring. 10 ℃
After cooling, the cake was washed with 300 g of methanol. The cake obtained is reduced pressure
Dried at 80 ° C. for 4 hours. After drying, melting point 101-1
10 ° C., epoxy equivalent 100 g / eq, hydrolyzable chlorine 800 ppm, average particle diameter 30 μm, epichlorohydrin 80 ppm remaining inside the crystal and methanol 1300 p
Tris- (2,3-epoxypropyl) containing pm
-820 g of isocyanurate crystals were obtained.

Example 1 β-type tris- (2,2) obtained by the recrystallization method obtained in Production Example 1
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 400 Nm ³ / h, a sample supply amount of 40 kg / h, and a classifying rotor at 5000 rpm. It was finely pulverized to an average particle size of 3.0 μm by pulverization and classification, and residual epichlorohydrin was reduced from 50 ppm to 20 ppm, and acetonitrile was reduced from 1360 ppm to 170 ppm.

Example 2 β-type tris- (2,2) obtained by the recrystallization method obtained in Production Example 2
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 400 Nm ³ / h, a sample supply amount of 40 kg / h, and a classifying rotor at 5000 rpm. It was finely pulverized to an average particle size of 3.0 μm by pulverization and classification, and the remaining epichlorohydrin was reduced from 50 ppm to 20 ppm, and the toluene was reduced from 1520 ppm to 200 ppm.

Example 3 β-type tris- (2,2) obtained by recrystallization obtained in Production Example 3
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 400 Nm ³ / h, a sample supply amount of 40 kg / h, and a classifying rotor at 5000 rpm. It was pulverized to an average particle size of 3.0 μm by pulverization and classification, and the remaining epichlorohydrin was reduced from 50 ppm to 20 ppm, and the dioxane was reduced from 1460 ppm to 210 ppm.

Example 4 β-type tris- (2,2) obtained by recrystallization obtained in Production Example 4
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 400 Nm ³ / h, a sample supply amount of 40 kg / h, and a classifying rotor at 5000 rpm. It was pulverized to an average particle size of 3.0 μm by pulverization and classification, and the remaining epichlorohydrin was reduced from 50 ppm to 20 ppm, and the dimethylformamide was reduced from 1800 ppm to 250 ppm.

Example 5 β-type tris- (2,2) obtained by the recrystallization method obtained in Production Example 5
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 400 Nm ³ / h, a sample supply amount of 40 kg / h, and a classifying rotor at 5000 rpm. The mixture was finely pulverized to an average particle size of 3.0 μm by pulverization and classification, and the remaining epichlorohydrin was reduced from 50 ppm to 20 ppm, and 1,2 dichloroethane was reduced from 1400 ppm to 180 ppm.

Example 6 Tris- (2,3-
(Epoxypropyl) -isocyanurate crystals by ALP
The powder was pulverized with an INE 200AFG type counter jet mill. Grinding is performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 40.
0 Nm ³ / h, the sample supply amount was 40 kg / h, and the classification rotor was operated at 5000 rpm. It is pulverized to a mean particle size of 3.0 μm by pulverization and classification, the remaining epichlorohydrin is reduced from 80 ppm to 30 ppm, and methanol is reduced to 1 ppm.
It was reduced from 300 ppm to 150 ppm.

Example 7 The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 1 was obtained from Alpine 2
It was pulverized with a 00AFG type counter jet mill. Grinding was performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 800 Nm ³ /.
h, the sample was supplied at a rate of 30 kg / h, and the mixture was pulverized at a classifying rotor of 12000 rpm. It was pulverized to an average particle size of 1.5 μm by pulverization, and the remaining epichlorohydrin was reduced from 50 ppm to 15 ppm, and acetonitrile was reduced from 1360 ppm to 80 ppm.

Example 8 The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 2 was obtained from Alpine 2
It was pulverized with a 00AFG type counter jet mill. Grinding was performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 800 Nm ³ /.
h, the sample was supplied at a rate of 30 kg / h, and the mixture was pulverized at a classifying rotor of 12000 rpm. It is pulverized to an average particle size of 1.5 μm by pulverization, remaining epichlorohydrin is reduced from 50 ppm to 15 ppm, and toluene is reduced to 152 ppm.
It was reduced from 0 ppm to 100 ppm.

Example 9 The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 3 was obtained from Alpine 2
It was pulverized with a 00AFG type counter jet mill. Grinding was performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 800 Nm ³ /.
h, the sample was supplied at a rate of 30 kg / h, and the mixture was pulverized at a classifying rotor of 12000 rpm. Pulverized by pulverization to an average particle size of 1.5 μm, remaining epichlorohydrin is reduced from 50 ppm to 15 ppm, and dioxane is reduced to 14 ppm.
It was reduced from 60 ppm to 110 ppm.

Example 10 The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 4 was obtained from Alpine 2
It was pulverized with a 00AFG type counter jet mill. Grinding was performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 800 Nm ³ /.
h, the sample was supplied at a rate of 30 kg / h, and the mixture was pulverized at a classifying rotor of 12000 rpm. It was pulverized to an average particle size of 1.5 μm by pulverization, and the remaining epichlorohydrin was reduced from 50 ppm to 15 ppm, and dimethylformamide was reduced from 1800 ppm to 200 ppm.

Example 11 The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 5 was obtained from Alpine 2
It was pulverized with a 00AFG type counter jet mill. Grinding was performed under a nitrogen pressure of 6.0 kg / cm ² and a nitrogen amount of 800 Nm ³ /.
h, the sample was supplied at a rate of 30 kg / h, and the mixture was pulverized at a classifying rotor of 12000 rpm. The mixture was pulverized to an average particle size of 1.5 μm by pulverization, and the remaining epichlorohydrin was reduced from 50 ppm to 15 ppm, and 1,2-dichloroethane was reduced from 1400 ppm to 90 ppm.

Example 12 The tris- (2,3-epoxypropyl) -isocyanurate crystal obtained in Production Example 6 was prepared using ALPINE 200
It was pulverized by an AFG type counter jet mill. The pulverization is performed under a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 800 Nm ³ / h, a sample supply amount of 30 kg / h, and a classifying rotor of 12 kg / h.
000 rpm and crushed. Pulverized to an average particle size of 1.5 μm by pulverization, the remaining epichlorohydrin is reduced from 80 ppm to 20 ppm, and methanol is reduced to 1300 ppm.
from 70 ppm to 70 ppm.

Example 13 The β-type tris- (2,2) obtained by the recrystallization method obtained in Production Example 1
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 200 Nm ³ / h, a sample supply amount of 60 kg / h, and a classification rotor at 5000 rpm. The mixture was finely pulverized to an average particle size of 20 μm by pulverization and classification. The remaining epichlorohydrin was reduced from 50 ppm to 30 ppm, and acetonitrile was reduced from 1360 ppm to 850 ppm.

Example 14 β-type tris- (2,2) obtained by recrystallization obtained in Production Example 5
3-epoxypropyl) -isocyanurate crystal
It was pulverized with a 200AFG type counter jet mill manufactured by LPINE. The pulverization was performed at a nitrogen pressure of 6.0 kg / cm ² , a nitrogen amount of 200 Nm ³ / h, a sample supply amount of 60 kg / h, and a classification rotor at 5000 rpm. It was pulverized to an average particle size of 18 μm by pulverization and classification, and the remaining epichlorohydrin was reduced from 50 ppm to 35 ppm, and 1,2-dichloroethane was reduced from 1400 ppm to 900 ppm.

[0065]

According to the present invention, the tris- (2,3-epoxypropyl) -isocyanurate crystal particles obtained by the recrystallization method are prepared by evaporating volatile components from the particle surface with an average particle diameter of 0.5 to 0.5. Tris by grinding to 20 μm
The residual organic solvent in the (2,3-epoxypropyl) -isocyanurate crystal can be removed.

The tris- (2,2) obtained by the conventional recrystallization method
In the 3-epoxypropyl) -isocyanurate crystal, the residual organic solvent taken into the crystal is removed by heating the organic solvent to a temperature higher than the melting point of tris- (2,3-epoxypropyl) -isocyanurate. Had been removed. The β-type tris- (2,3-epoxypropyl) -isocyanurate crystals required heating at a high temperature of 150 ° C. or higher.

Further, from the reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate, β-type tris- (2,3-α-type containing tris- (2,3-epoxypropyl) -isocyanurate was used. 3-epoxypropyl) -isocyanurate crystals are also used for the precipitation.
Heating to a temperature of from 00 to 140 ° C., preferably from 120 to 140 ° C. to melt the α-form tris- (2,3-epoxypropyl) -isocyanurate in the crystal to form a molten portion formed in the crystal It is also possible to remove the organic solvent (epichlorohydrin and the organic solvent used for recrystallization) by passing through, but in the present invention, the tris- (2,
The organic solvent could be removed only by pulverizing the 3-epoxypropyl) -isocyanurate crystal in a stream. In particular, β-type tris- (2,3-epoxypropyl)-
It is effective for removing the residual organic solvent from the isocyanurate crystals.

Claims (9)

[Claims] 1. The method of claim 1, wherein the tris- (2,3-
Tris- (2,3-epoxypropyl)-by pulverizing the epoxy particles) -isocyanurate crystal particles as a raw material while evaporating volatile components from the particle surface.
A method for reducing a residual organic solvent in an isocyanurate crystal. 2. A raw material of tris- (2,3-epoxypropyl) -isocyanurate crystal particles is reacted with cyanuric acid and epichlorohydrin in the presence of a catalyst to obtain a chlorohydrin ester of isocyanuric acid. ,
The alkali metal chloride formed by dehydrochlorination with an alkali is separated, and the solvent is removed from the reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate to obtain tris- (2,3-epoxy). (Propyl) -isocyanurate is obtained by recrystallization using a solvent.
5. The method for reducing residual organic solvent according to the above. 3. The method according to claim 1, wherein the recrystallization solvent is acetonitrile, dichloroethane, dioxane, toluene, dimethylformamide, methanol, ethanol, or isopropyl alcohol. 4. The pulverization in which volatile components evaporate from the particle surface is pulverization performed in an air stream.
The method for reducing a residual organic solvent according to any one of the above. 5. The crystalline particles having an average particle size of 0.5 to 20 μm.
The method for reducing residual organic solvent according to any one of claims 1 to 4, wherein the method is pulverized to m. 6. The method for reducing a residual organic solvent according to claim 1, wherein the concentration of the residual organic solvent is 300 ppm or less. 7. Tris- (2,3-epoxypropyl)
-Isocyanurate crystal particles are β-tris- (2,
The method for reducing residual organic solvent according to any one of claims 1 to 6, wherein the particles are crystalline particles of (3-epoxypropyl) -isocyanurate. 8. The method according to claim 7, wherein the recrystallization solvent is acetonitrile, dichloroethane, dioxane, toluene, or dimethylformamide. 9. The method for reducing residual organic solvent according to claim 1, wherein the residual organic solvent is epichlorohydrin and acetonitrile.