JP2000007672A - Beta-type tris-(2,3-epoxypropyl)-isocyanurate crystal and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain highly pure β-type tris-(2,3-epoxypropyl)-isocyanurate crystals from which injurious epichlorohydrin is reduced, and to obtain a method for producing the same. SOLUTION: β-Type tris-(2,3-epoxypropyl)-isocyanurate crystals containing α-type tris-(2,3-epoxypropyl)-isocyanurate in the crystals. The crystals are produced by (A) a process for reacting cyanuric acid with epichlorohydrin to obtain the reaction solution containing tris-(2,3-epoxypropyl)-isocyanurate, (B) a process for adjusting the concentration of solid contents, (C) a process for adding seed crystals, (D) a process for cooling the mixture to obtain the crystals, and (E) a process for washing and drying the crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a β-type tris- (2,
The present invention relates to a crystal of 3-epoxypropyl) -isocyanurate and its production, wherein the content of α-form tris- (2,3-epoxypropyl) -isocyanurate in the form of being present on the surface of the crystal and being extracted into alcohol is as follows. 2% by weight
The present invention relates to a method for efficiently producing epichlorohydrin as a high-purity product in which epichlorohydrin, which is harmful to human bodies and electronic materials, is reduced to 1000 ppm or less.

[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, soldering 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 equipment, lower bleeding when forming solder resist patterns for surface mounting of components, and more precise embedding between circuits has been increasing. ing. Therefore, as the 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 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)
A crystal which is an equimolar mixture of -isocyanurate and (2S, 2'S, 2 "S) -tris- (2,3-epoxypropyl) -isocyanurate is generally called a β-type crystal and has 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 hydrogen bonds in pairs, forming 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-type 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-setting / thermo-setting solder resist ink composition.

The liquid epoxy composition may increase the viscosity during storage due to the dissolution of a part of the epoxy compound in the solvent, and 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 reduce 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 eroded by a developer 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 is relatively well dissolved, and β-type tris- (2,3-epoxypropyl) -isocyanurate is difficult to dissolve in a solvent, for example, a resolution method using an alcohol such as methanol. was there. For example, the Journal of Thermal Analysis (J
In ournal of Thermal Analysis, Vol. 36 (1990), p. 1819, the separation is carried out using a methanol solvent. Also, Plaste und Kautschuk
23 In Jahrgang Heft4 / 1975, first, β-type tris- (2,3-epoxypropyl)-
After splitting the isocyanurate, β-tris- (2,3
-Epoxypropyl) -isocyanurate is purified with chloroform. In addition, Vol. 47, No. 3 (19
90) On page 169, tris- (2,3-epoxypropyl) -isocyanurate obtained by synthesis is put into methanol, heated and stirred, and the undissolved matter is filtered off. Recrystallize with methyl ethyl ketone to give β-tris-
(2,3-Epoxypropyl) -isocyanurate crystals are obtained.

Most of the β-type tris- (2,3-epoxypropyl) -isocyanurate obtained by such a dividing method has difficulty in crystal growth, and many have an average particle diameter of less than 10 μm. In the filtration step, if the pore size of the filter medium is 10 μm or more, much of the material passes through the filter medium, and the yield is significantly impaired. Make it difficult.

[0007] In one division operation of the above division method, β-tris- (2,3-epoxypropyl)-
Chlorine-containing impurities and other impurities in isocyanurate, α
Since it is easy to include the type tris- (2,3-epoxypropyl) -isocyanurate, it is necessary to further perform recrystallization.

[0008]

[Problems to be Solved by the Invention] JP-B-48-2403
In No. 9, chlorohydrin ester of isocyanuric acid obtained by reacting cyanuric acid with epichlorohydrin is
The alkali metal chloride produced by dehydrochlorination with an alkali is separated, and the resulting tris- (2,3-epoxypropyl)-
The solution of isocyanurate in epichlorohydrin is concentrated to a concentration of tris- (2,3-epoxypropyl) -isocyanurate of 50 to 60%, and then cooled to 20 to 25 ° C to obtain a tris- ( 2,3-Epoxypropyl) -isocyanurate crystals are obtained. Tris- (2,3-epoxypropyl) -isocyanurate obtained by a known production method is α-form tris- (2,3
-Epoxypropyl) -isocyanurate and β-form tris- (2,3-epoxypropyl) -isocyanurate in a ratio of 3: 1.

The β-type tris- (2,3-epoxypropyl) -isocyanurate present in the reaction stage of JP-B-48-24039 can be expected to have a yield based on cyanuric acid of 20% or less. In a later stage, the yield based on cyanuric acid can be expected to be 19% or less. However, the tris- (2,2) obtained in Japanese Patent Publication No.
3-epoxypropyl) -isocyanurate crystals
Calculated from the yield based on cyanuric acid of 27%, the ratio of α-type tris- (2,3-epoxypropyl) -isocyanurate in the obtained crystal was at least (2
7% -19%) / 27% × 100 = 30%. The results of the additional tests we performed also showed that α-type tris- (2,
A result in which the content of (3-epoxypropyl) -isocyanurate was 30% or more was obtained. Tokiko 48-24039
Many crystals of α-type tris- (2,3-epoxypropyl) -isocyanurate contain β-type tris-
It is considered that it is attached to the surface of the (2,3-epoxypropyl) -isocyanurate crystal or exists as a single crystal.

Therefore, in the above-mentioned method, a large amount of α-form tris- (2,3-epoxypropyl) -isocyanurate which is extracted into alcohol is contained, and further, several thousand ppm of epichlorohydrin and the like are contained in the crystal. There is a problem of being included. That is, as described above, α-type tris- (2,3-epoxypropyl) -isocyanurate, which is soluble in alcohol, becomes β-type tris- (2,3-
Since it is present on the surface of (epoxypropyl) -isocyanurate crystal or present alone, there is a problem that it dissolves in the solder resist composition to lower the storage stability and the developability. 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.

An object of the present invention is to provide an industrially advantageous tris-
The present invention relates to β-type tris- (2,3-epoxypropyl) -isocyanurate obtained by crystallization of a (2,3-epoxypropyl) -isocyanurate reaction solution,
Α-type tris- (2,3-
Epoxypropyl) -isocyanurate is all tris-
(2,3-epoxypropyl) -isocyanurate 2
100% by weight or less of residual epichlorohydrin
An object is to obtain β-type tris- (2,3-epoxypropyl) -isocyanurate reduced to 0 ppm or less, particularly 300 ppm or less.

[0012]

Means for Solving the Problems A first aspect of the present invention is as follows.
β-type tris- (2,3-epoxypropyl) -isocyanurate crystal containing α-type tris- (2,3-epoxypropyl) -isocyanurate in the crystal at a ratio of 2 to 15% by weight, the present invention The second aspect of the invention is that the average particle diameter of the crystal is 10 to 500 μm.
Type tris- (2,3-epoxypropyl) -isocyanurate crystal, a third aspect of the present invention provides the following (A):
Steps (B), (C), (D) and (E): Step (A): reacting 1 mol of cyanuric acid with 5-180 mol of epichlorohydrin to form an epichlorohydrin adduct of cyanuric acid, Step of obtaining a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate by dehydrochlorination, Step (B): Tris- (2,3- obtained in step (A)
A step of preparing a reaction solution containing (epoxypropyl) -isocyanurate to a solid content concentration of 10 to 50% by weight; step (C): the liquid obtained in step (B) is a saturated solution (C) a step of adding a seed crystal at a temperature 5 to 20 ° C. lower than the temperature at which the liquid is formed.
α-type tris- (2, a step of slowly cooling at a cooling rate within hr to obtain a crystal by filtration and a step of washing and drying the crystal obtained in the step (E): step (D). A method for producing a β-type tris- (2,3-epoxypropyl) -isocyanurate crystal containing 3-epoxypropyl) -isocyanurate in the crystal at a ratio of 2 to 15% by weight, a fourth aspect of the present invention. Is that (A) is a process wherein (a) 1 mol of cyanuric acid, (b) 5-180 mol of epichlorohydrin, and (c) a tertiary amine, a quaternary ammonium salt, a quaternary ammonium base, A reaction solution obtained by reacting 0.001 to 0.1 mol of at least one compound selected from the group consisting of phosphine and a quaternary phosphonium salt is added to an alkali metal hydroxide or an alkali metal hydroxide. The production method according to the third aspect, which is a step of adding 2 to 6 mol of an alcoholate, dehydrochlorinating, and removing an alkali metal salt to obtain a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate. According to a fifth aspect of the present invention, in the step (C), the temperature of the liquid obtained in the step (B) is raised to a temperature higher than a temperature at which a saturated solution is formed, and then the temperature is increased by 5 to 20 to a temperature at which a saturated solution is formed. The method according to the third aspect or the fourth aspect, in which the seed crystal is cooled to a low temperature and then the seed crystal is added, and the sixth aspect of the present invention is that the addition of the seed crystal in the step (C) is performed according to the following formula ( 1) and (2)

[0013]

1 × 10 ¹⁰ ≧ T ≧ 1 × 10 ² Equation (1)

[0014]

T = 1.4 × 10 ¹² (m / (M × D ³ )) Formula (2) [where T is based on the weight of tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution] , The number (g) of seed crystals added, m is the average particle size of seed crystals, D is 2 to 300 μm, and M is tris- (2,3- (Epoxypropyl) -isocyanurate weight (g). The method according to any one of the third to fifth aspects, wherein the seed crystal added in the step (C) is β-type tris- (2,
3-epoxypropyl) -isocyanurate or a mixture of β-type tris- (2,3-epoxypropyl) -isocyanurate and α-type tris- (2,3-epoxypropyl) -isocyanurate from the third viewpoint to the third aspect. The manufacturing method according to any one of the six aspects, and an eighth aspect of the present invention is directed to the third aspect to the seventh aspect in which ultrasonic waves are applied to the liquid in the process of gradually cooling the liquid in the step (D). According to a ninth aspect of the production method described in any one of the first to fourth aspects of the present invention, the washing in the step (E) is performed by adding 0.5 g of α-type tris- (2,3-epoxypropyl) -isocyanurate at 20 ° C / 100 g or more and 0.1% at 20 ° C. for β-tris- (2,3-epoxypropyl) -isocyanurate.
Any one of the third to eighth aspects in which a solvent having a solubility of less than 5 g / 100 g is used in an amount of 0.5 to 10 times by weight the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal. According to a tenth aspect of the present invention, the crystal obtained in the step (D) has an average particle diameter of 20 to 500 μm, and in the step (E), the crystal is obtained in an air stream under normal pressure or reduced pressure. The method according to any one of the third to ninth aspects in which drying is performed at a temperature of 120 to 140 ° C., and the eleventh aspect of the present invention relates to a method of drying the crystal obtained in the step (D). The average particle diameter is 10 to 20 μm, and in the step (E), it is 40 to 120 in an air stream under normal pressure or reduced pressure.
The manufacturing method according to any one of the third to ninth aspects, wherein drying is performed at a temperature of ° C.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The α-type tris- (2,3
Β-tris- (2,3-epoxypropyl) -isocyanurate containing 2 to 15% by weight of a crystal in the crystal.
3-epoxypropyl) -isocyanurate crystals
It is obtained as an average particle diameter of 10 to 500 μm. β-type tris- (2,3-epoxypropyl) -α-type tris present inside the isocyanurate crystal
The content of (2,3-epoxypropyl) -isocyanurate is 2 to 15% by weight, preferably 4 to 13% by weight in the ratio of (α form) / (α form + β form).

The α-form tris- (2,3-epoxypropyl) present on the surface of the β-form tris- (2,3-epoxypropyl) -isocyanurate crystal of the present invention or alone.
As a method for measuring the isocyanurate content, for example, there is a solvent extraction method, and the β-form has a very low solubility in an organic solvent compared to the α-form, so that it can be accurately measured. Examples of the organic solvent used here include alcohol solvents such as methanol and ethanol.

As a method for measuring the ratio of α-form and β-form of the whole crystal, there is, for example, a method by ¹ H-NMR, IR or HPLC using a column for optical resolution. The column for optical resolution can be efficiently separated by using amylose or a cellulose derivative for the stationary phase, and can be measured with high accuracy.

The α-form tris- (2,3-epoxypropyl) -isocyanurate contained in the β-form tris- (2,3-epoxypropyl) -isocyanurate crystal of the present invention is 2 to 15% by weight. The analysis method is not limited to the method described in the present application.

The α-type tris- (2,3-epoxypropyl) -isocyanurate contained in the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal is extracted with an organic solvent such as methanol. Therefore, when the epoxy resin composition is used, it is not eluted from the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal.

In the method of the present invention for producing a β-form tris- (2,3-epoxypropyl) -isocyanurate crystal, the step (A) comprises one mole of cyanuric acid and 5-180
In this step, an epichlorohydrin adduct of cyanuric acid is produced by reacting with mol epichlorohydrin, followed by dehydrochlorination to obtain a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate.
More specifically, step (A) comprises (a) 1 mol of cyanuric acid, (b) 5-180 mol of epichlorohydrin, and (c) a tertiary amine, a quaternary ammonium salt, and a quaternary ammonium base as a catalyst. , A tri-substituted phosphine, and a reaction solution obtained by reacting 0.001 to 0.1 mol of at least one compound selected from the group consisting of quaternary phosphonium salts, with an alkali metal hydroxide or After adding 2 to 6 mol of an alkali metal alcoholate and dehydrochlorinating,
This is a step of obtaining a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate by removing the alkali metal salt.

The catalyst for adding epichlorohydrin to cyanuric acid in the step (A) is not particularly restricted but includes, for example, tertiary amines, quaternary ammonium salts, quaternary ammonium bases, trisubstituted phosphines, and Quaternary phosphonium salts, such as cyanuric acid 1
It is preferable to use 0.001 to 0.1 mole of the catalyst based on the mole. Examples of catalysts include tertiary amines such as tripropylamine, tributylamine, N, N '
-Dimethylpiperazine and the like. 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, and examples of the quaternary phosphonium salt include tetramethylphosphonium halide, tetrabutylphosphonium halide, and methyltriphenyl. Examples thereof include phosphonium halide and ethyltriphenylphosphonium halide. Examples of the halide include chloride, bromide, and iodide. Among the compounds mentioned here, quaternary ammonium salts and quaternary phosphonium salts are preferable because the reaction proceeds efficiently under less mild conditions with less side reactions. Particularly preferred are quaternary ammonium salts, among which tetramethylammonium halide, tetraethylammonium halide, and tetrabutylammonium halide are used. As the halide, chloride and bromide are used, 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.

Further, in the step (A), a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate is obtained by subsequent dehydrochlorination. The reagent used in the dehydrochlorination reaction is not particularly limited, and examples thereof include an alkali metal hydroxide or an alkali metal alcoholate. It is preferably used in the range of 2 to 6, preferably 2.5 to 4 mol. Examples of the above alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide, and examples of the alkali metal alcoholate include sodium methylate, sodium ethylate, potassium methylate, and potassium ethylate. .
The tris- (2,3-epoxypropyl) -isocyanurate thus formed includes β-type tris- (2,3-epoxypropyl) -isocyanurate and α-type tris-
It contains (2,3-epoxypropyl) -isocyanurate in a weight ratio of 1: 3.

The tris- (2,3) thus obtained
The reaction solution containing (-epoxypropyl) -isocyanurate is adjusted to a concentration suitable for crystallization by concentration or dilution. The solid content can be measured by performing a treatment at 120 ° C. and 5 Torr or less for 3 hours with a rotary evaporator to dryness, and measuring the weight of the solid content to calculate the solid content.

In the step (B), the solid content of the reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate is 10% by weight to 50% by weight, preferably 25% by weight.
It is adjusted to 40% by weight.

If the concentration is too low, the cooling temperature required for crystallization must be cooled to a low temperature, and a sufficient yield cannot be obtained.

Conversely, if the concentration is too high, the cooling temperature required for crystallization must be maintained at a high temperature, and as a result, the filtration temperature must be maintained at a high temperature. At this time, when cooled to a temperature lower than the final cooling temperature range, rapid crystallization occurs, and α-form tris- (2,3-epoxypropyl)-
It is not preferable because isocyanurate is easily taken in. On the other hand, when the concentration is too high, the change in solubility with respect to the temperature change is large, so that rapid crystallization occurs, and α-type tris- (2,
It is not preferable because 3-epoxypropyl) -isocyanurate is easily taken in.

The necessity of maintaining the cooling temperature range necessary for the crystallization is to selectively contain an appropriate amount of the α-form in the crystallized β-form.

Table 1 shows the tris- (2,3-epoxypropyl) -isocyanurate solid concentration (%) in the reaction solution.
And the temperature (° C.) for forming a saturated solution and the cooling temperature (° C.) required for crystallization. Here, the temperature at which a saturated solution is formed means that the reaction solution obtained in the step (B) is heated to 120 ° C.
Tris- (2,3-epoxypropyl) -isocyanurate obtained by drying at 2 Torr was pulverized to obtain a powder having a size of 32 mesh or less. The temperature was further increased at a rate of 1 ° C./min to obtain the temperature at the time of complete dissolution.

[0029]

[Table 1] Table 1 ――――――――――――――――――――――――――――――――――― TRIS-(2,3-Ethoxyfluorophenyl) )-Isocyanurate solid content concentration (%) 50 40 30 25 15 10 ―――――――――――――――――――――――――――――――――― ― Temperature to form saturated solution (℃) 79 69 58 53 39 29 Cooling temperature required for crystallization (℃) 35 ± 5 25 ± 5 15 ± 5 11 ± 5 0 ± 5 −5 ± 5 ――――― ―――――――――――――――――――――――――――――― In the process (C), the liquid obtained in the process (B) is added to the liquid The seed is seeded at a temperature 5-20 ° C below the temperature at which the product forms a saturated solution. If crystallization is performed without adding seed crystals, the supersaturated state continues even during cooling, and crystallization occurs at a stretch in the latter half of cooling. This is because epichlorohydrin and α-type tris- (2,
Unpreferable, for example, the purity is lowered due to the incorporation of impurities such as 3-epoxypropyl) -isocyanurate.

In the step (C), before the seed crystal is added, the reaction solution is heated to a temperature not lower than a temperature at which a saturated solution is formed, so that tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution is removed. After sufficient dissolution, the seed crystals can be added by slow cooling to a temperature 5-20 ° C. below the temperature at which the saturated solution is formed. This method is preferable in terms of filterability and the like because the obtained crystal has a uniform particle size.

In step (C), the seed crystal is added according to the following formula (1)
And (2) 1 × 10 ¹⁰ ≧ T ≧ 1 × 10 ² Equation (1) T = 10 ¹² m / (M (4/3) π (D / 2) ³ d) = 1.4 × 10 ¹² (m / (M × D ³ )) Formula (2) [where T is the number of seed crystals added per weight of tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution (pieces / g), m Is the weight of the seed crystal added (g), D is the average particle diameter of the seed crystal, 2 to 300 μm, M is the weight (g) of tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution, and d is the weight of tris It is the true specific gravity of-(2,3-epoxypropyl) -isocyanurate. ].

In the present invention, crystal growth starts with the added seed crystal as a nucleus. The crystal size of the resulting β-form tris- (2,3-epoxypropyl) -isocyanurate is determined by the tris-
It is controlled by the number of seed crystals added per (2,3-epoxypropyl) -isocyanurate weight (T: number / g). The number (T) of seed crystals determined by the amount of seed crystals added and the average particle size is determined by using tris- (2,3-epoxypropyl) -isocyanate in the reaction solution when seed crystals having an average particle size of 2 to 300 μm are used. 10 ² / g per weight of nurate
The above is preferred. When the number of seed crystals is small, the average crystal size of the crystallized β-type tris- (2,3-epoxypropyl) -isocyanurate is larger, and when the number of seed crystals (T) is large, the average crystal size is smaller. β-type tris- (2,3-epoxypropyl) -isocyanurate crystals are crystallized. The number of seed crystals (T) is 1 × 10
Β-type tris which is crystallized when the amount is more than ¹⁰ particles / g
The average particle diameter of (2,3-epoxypropyl) -isocyanurate is less than 10 μm, which is not preferable. In particular, when a seed crystal having an average particle diameter exceeding 100 μm is used and the number (T) of the seed crystals is increased, the added weight is too large, which is not preferable.

If the step (C) is not heated above the temperature at which a saturated solution is formed but is maintained at a temperature 5 to 20 ° C. lower than the temperature at which a saturated solution is formed, at this temperature fine crystallites are contained in the reaction solution. Is generated, and this crystal together with a seed crystal added later also functions as a seed crystal, and it is difficult to control the number (T) of the seed crystals. Therefore, once heated to a temperature above the temperature at which a saturated solution is formed, then 5 to 5 degrees below the temperature at which a saturated solution is formed.
It is more desirable to cool to a temperature lower by 20 ° C. and to add seed crystals.

The seed crystal added in the step (C) is β-tris-
It is possible to use (2,3-epoxypropyl) -isocyanurate or a mixture of β-type tris- (2,3-epoxypropyl) -isocyanurate and α-type tris- (2,3-epoxypropyl) -isocyanurate. it can.

After the seed crystal is added in step (C), stirring is preferably performed at the added temperature for 0.5 to 1 hour.

Then, as a step (D), α-tris-
Slowly cool to a temperature at which (2,3-epoxypropyl) -isocyanurate maintains a supersaturated state. This cooling rate is within 20 ° C./hr, preferably within 10 ° C./hr. Rapid cooling is not preferred because rapid crystal precipitation occurs and purity is reduced due to the incorporation of impurities.

The crystallized β-form tris- (2,3-epoxypropyl) -isocyanurate crystal is filtered off by suction filtration, filter press method, centrifugal filtration method or the like.

In the step (E), the β-type tris- (2,3-epoxypropyl) -isocyanurate filtered off contains impurities, α-type tris- (2,3-epoxypropyl) -isocyanurate and epichlorohydrin. Since it is contained, it can be washed with various organic solvents. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, acetonitrile, dimethylformamide, epichlorohydrin and the like. The solubility is less than 0.5 g / 100 g, and the α-form Tris-
Organic solvents having a solubility in (2,3-epoxypropyl) -isocyanurate at 20 ° C. of 0.5 g / 100 g or more are preferred. Examples of the organic solvent having such characteristics include methanol, ethanol, and isopropyl alcohol.

The washing can be carried out at a temperature of 5 to 50 ° C., preferably 5 to 30 ° C. High temperature, for example, 30-50 ° C
Increases the solubility and saves solvent usage,
Operation at a temperature close to the flash point or boiling point. A centrifugal filter may cause an accident due to ignition of static electricity.
(2,3-epoxypropyl) -isocyanurate is
Aeration of the pressurized gas may cause re-precipitation in the filter medium or cake, which may reduce the filterability. In addition, α-tris- (2,3-epoxypropyl)-
There are restrictions such as the necessity of a heat retaining facility for preventing isocyanurate from reprecipitating. Above 50 ° C., a special thermal filtration system is required. If the temperature is lower than 5 ° C., a large amount of solvent is required.

The washing amount varies depending on the temperature and the solvent.
0.5 to 10 times the dry weight of the type tris- (2,3-epoxypropyl) -isocyanurate crystals,
Preferably it is 1 to 6 times by weight. As a washing method, the β-type tris- (2,3-epoxypropyl) -isocyanurate which has been separated by filtration can be slurried again and filtered, or it can be washed by passing it while filtering.

In the step (E), after washing, drying can be performed at 120 to 140 ° C. in an air stream under normal pressure or reduced pressure. The above-mentioned reduced pressure can be performed at various pressures as long as the pressure is lower than normal pressure, for example, 5 to 20 Torr.
Can be exemplified. The drying time is 2 to 24.
Time.

The above-mentioned temperature of 120 to 140 ° C. is a temperature not lower than the melting point of α-type tris- (2,3-epoxypropyl) -isocyanurate and β-type tris- (2,3
-Epoxypropyl) -isocyanurate. By drying in an air stream at this temperature, α
Β-type tris- (2,3-epoxy) containing tris- (2,3-epoxypropyl) -isocyanurate in the crystal body
In the (epoxypropyl) -isocyanurate crystal, a portion of the α-type tris- (2,3-epoxypropyl) -isocyanurate melts and becomes liquid. Through this liquid portion, the epichlorohydrin impurity is discharged from the crystal to the outside of the crystal. Β-type tris- (2,3) containing α-type tris- (2,3-epoxypropyl) -isocyanurate obtained through the drying step (E) at a ratio of 5 to 15% by weight inside the crystal. -Epoxypropyl)-
The isocyanurate crystal can reduce the residual epichlorohydrin to 1000 ppm or less, particularly preferably 300 ppm or less. The amount of residual epichlorohydrin in the product was determined by determining the amount of α-form tris- (2,
3-epoxypropyl) -isocyanurate is from 120 to
It melts at a drying temperature of 140 ° C., preferably 125 to 135 ° C. to form liquid pores inside the crystal, and epichlorohydrin is discharged out of the crystal through the liquid pores. . In order to reduce the residual epichlorohydrin, an appropriate amount of α-type tris-
(2,3-epoxypropyl) -isocyanurate;
Appropriate washing and drying methods are considered necessary. In particular, a crystal having an average particle diameter of 20 to 500 μm is in the range of 120 to 14
Since the amount of residual epichlorohydrin is significantly reduced before and after drying at 0 ° C., it is necessary to dry crystals having an average particle size of 20 to 500 μm at 120 to 140 ° C. under normal pressure or reduced pressure in an air stream.

The α-form tris- (2,
When the content of (3-epoxypropyl) -isocyanurate is less than 2% by weight, α-tris-
(2,3-Epoxypropyl) -isocyanurate has few loopholes due to melting, and the amount of residual epichlorohydrin in the formed crystal increases.

The α-type tris present in the crystal body
If the content of (2,3-epoxypropyl) -isocyanurate exceeds 15% by weight, α-type tris- (2,3-epoxypropyl) -isocyanurate oozes from the inside of the crystal at the time of drying at 120 to 140 ° C. It becomes a binder between particles and causes agglomeration, which is not preferable. If the agglomeration of the particles occurs, the drying efficiency is poor, the discharge from the dryer becomes difficult, and it is not preferable because new pulverization is required.

However, α-type tris- (2,3
-Epoxypropyl) -isocyanurate content is 2
If the drying temperature is 120 to 140 ° C. at １５15% by weight and the α-type tris- (2,3-epoxypropyl) -isocyanurate bleeds to the surface of the crystal particles, the crystal is hardly aggregated.

The amount of α-type tris- (2,3-epoxypropyl) -isocyanurate in the form of a crystal or on the surface of a single crystal and extracted into alcohol is preferably 2% by weight or less. When this value exceeds 2% by weight, the crystal shape and the particle size distribution become non-uniform, so that the filterability is lowered and the particles are liable to aggregate during drying. Also light curing
When a heat-curable combined one-part resist ink composition is used, it melts in a solvent and thickens during storage, or causes cling with a photosensitive prepolymer, so that the unexposed part after exposure is washed away. Elution may be poor.

When the amount of α-form tris- (2,3-epoxypropyl) -isocyanurate which is present on the surface of the crystal or alone and extracted into alcohol slightly exceeds 2% by weight, additional washing with methanol or the like is carried out. Although it is possible to reduce this value to 2% by weight or less,
In the case of 20% by weight, the additional washing amount of methanol at 20 ° C. needs to be 20 to 40 times by weight, which is an extremely inefficient method in consideration of working efficiency and recovery or disposal of methanol. Washing with warm methanol can save the amount of methanol used.However, a centrifugal filter cannot be used and a pressurized filter must be used. -(2,3-Epoxypropyl) -isocyanurate is reprecipitated in the filter medium or cake, so that the filterability is deteriorated and there is a restriction on equipment.

According to the invention of the present application, when vigorous stirring, for example, ultrasonic vibration is applied during the crystallization in the step (D), 10 μm to 50 μm
m, especially crystals having an average particle size of 10 μm to 20 μm are crystallized. When the average particle diameter of the crystal obtained in the step (D) is 10 to 20 μm, the α in the step (D)
The re-dissolution of type tris- (2,3-epoxypropyl) -isocyanurate is apt to occur, and the large specific surface area of the crystal in step (E) causes α-type tris- (2,2).
Since the (3-epoxypropyl) -isocyanurate is easily removed by washing with an organic solvent, the crystal obtained in the step (E) contains α-type tris- (2,3-epoxypropyl) contained inside the crystal. -The isocyanurate content is as low as 2 to 5% by weight. The crystals are dried at a temperature lower than the melting point of α-form tris- (2,3-epoxypropyl) -isocyanurate, for example, at 40 to 120 ° C. in an air stream under normal pressure or reduced pressure to remove residual epichlorohydrin by 400 ppm. It can be reduced below. Although this method is insufficient in terms of residual epichlorohydrin as compared with a method of drying at a temperature equal to or higher than the melting point of α-type tris- (2,3-epoxypropyl) -isocyanurate, the drying method can be simplified. . However, this crystal is also heated in a gas stream under normal pressure or reduced pressure to a temperature higher than the melting point of α-form tris- (2,3-epoxypropyl) -isocyanurate (1
By drying at 20 to 140 ° C.), residual epichlorohydrin can be reduced to 300 ppm or less.

<Method for quantifying α-type tris- (2,3-epoxypropyl) -isocyanurate in the crystal> (1) α-type tris- (2,3-
Epoxypropyl) -isocyanurate is prepared by adding 10 times the amount of methanol to a sample (crystal),
After stirring for 0 minutes, tris- (2,3
-Epoxypropyl) -isocyanurate by HPLC
(High performance liquid chromatography).

When a value of 10% by weight or more is obtained under these conditions, the processing temperature is changed from 20 ° C. to 40 ° C., and the measurement is performed in the same manner.

The tris which can be extracted into methanol
(2,3-epoxypropyl) -isocyanurate is α-form tris- (2,3-epoxypropyl) -isocyanurate present on the surface of the crystal. (2) The method for measuring the ratio of α-type and β-type in the whole crystal is as described in HP
Optical separation column CHIRALPAK A available on LC
D (manufactured by Daicel Chemical Industries, Ltd. (0.46 cm diameter x 25)
cm)), n-hexane / 2-propanol (40/60 v / v) as eluent, column temperature 24
° C, flow rate 1.0 ml / min. The crystals of the sample were dissolved in acetonitrile, diluted with an eluent, injected into HPLC, and subjected to chromatographic separation to obtain 11.00 β-tris- (2,3-epoxypropyl) -isocyanurate. Min and 16.80 min, and α-form tris- (2,3-epoxypropyl) -isocyanurate elutes at 12.87 min and 14.20 min. The ratio of α-form and β-form in the whole crystal was calculated from the area ratio of each peak.

Α-type tris which cannot be extracted with methanol
(2,3-epoxypropyl) -isocyanurate is
It can be calculated by the above (2)-(1). The α-type tris- (2,3-epoxypropyl) -isocyanurate which cannot be extracted into methanol is formed by the α-type tris- (2,3-epoxypropyl) present inside the β-type crystal.
-Considered an isocyanurate.

<Method for Quantifying Unreacted Epichlorohydrin Remaining in Crystal> The unreacted epichlorohydrin remaining in the crystal was added to a sample (crystal) by adding 20 times the amount of dimethylformamide, and added at 80 ° C. It can be dissolved by heating and quantified by gas chromatography.

<Measurement of Average Particle Size and Particle Size Distribution> The measurement was carried out by a wet method using a laser diffraction light scattering particle size distribution measuring apparatus using methanol as a dispersion medium. As the average particle diameter, a volume-based median diameter (median diameter) D50 was used. The particle size (D10) at the time of 10% cumulative volume and the particle size (D90) at the time of 90% cumulative volume are shown as numerical values representing the distribution.

[0055]

EXAMPLE 1 Step (A): 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 a reaction system, The reaction was carried out by adding 774 g (6 mol) of cyanuric acid, 8328 g (90 mol) of epichlorohydrin, and 213 g of an aqueous solution of tetramethylammonium chloride having a concentration of 15.5% by weight, and refluxing the mixture at 89 to 120 ° C. for 5 hours while stirring. Next, the temperature of the reaction system was cooled to 50 ° C., and 1536 g of a 50% by weight aqueous sodium hydroxide solution was reacted with stirring at a reduced pressure of 100 to 60 Torr for 6 hours while maintaining the temperature at 50 ° C. for dehydrochlorination. Thereafter, the resulting sodium chloride was washed by adding and dissolving 3600 g of water, and then separated, and further washed by adding 1200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate.
Neutralize the excess sodium hydroxide used, then
Washed with 00 g of water. Step (B): A portion of epichlorohydrin was distilled off under reduced pressure at a temperature of 50 to 60 ° C. until the solid concentration in the reaction solution became 40% by weight, to obtain 4000 g of a prepared solution. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-type tris- (2,3- 11.2 g (epoxypropyl) -isocyanurate (the number T of seed crystals was 1 × 10 ⁵ / g) was added. Step (D): After stirring at 60 ° C for 1 hour, cooling to 25 ° C in 4 hours, β-tris- (2,3-epoxypropyl)
-Isocyanurate crystals were precipitated and separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 280 g. The obtained crystal had a residual epichlorohydrin amount of 700 ppm and an epoxy value of 101 g.
/ Eq. Α-tris- (2,
(3-epoxypropyl) -isocyanurate content is 0.
The content of α-type tris- (2,3-epoxypropyl) -isocyanurate, which is contained in the crystal and cannot be extracted with methanol, is 7.7% by weight, and the crystal has a melting point of 148 to 158 ° C. The average particle diameter was 75 μm, and the particle size distribution was D10 of 12 μm, D50 of 75 μm,
90 was 180 μm and white crystals. Further, β-crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours.
The type tris- (2,3-epoxypropyl) -isocyanurate crystal has a residual epichlorohydrin content of 180 pp.
m.

Example 2 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-type tris- (2, 3-Epoxypropyl) -isocyanurate was added in an amount of 11.2 g (the number of seed crystals T was 4.9 × 10 ⁸ / g). Step (D): The same operation as in Example 1 was performed. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 290 g. The obtained crystal had a residual epichlorohydrin amount of 330 ppm and an epoxy value of 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% By weight, containing 4.1% by weight of α-form tris- (2,3-epoxypropyl) -isocyanurate which cannot be extracted with methanol, and has a melting point of 149 to 158 ° C. In addition, the average particle diameter was 15 μm, and the particle size distribution was D10: 8 μm, D50: 15 μm, D90: 25 μm, and white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin amount of 190 ppm. Met.

Example 3 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-type tris- (2, 24.0 g (3-epoxypropyl) -isocyanurate (the number T of seed crystals was 1.05 × 10 ⁹ / g) was added. Step (D): The same operation as in Example 1 was performed. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 310 g. The obtained crystal had a residual epichlorohydrin amount of 270 ppm and an epoxy value of 101 g /.
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% By weight, the content of α-tris- (2,3-epoxypropyl) -isocyanurate which is contained in the crystal and cannot be extracted with methanol is 3.2% by weight. The average particle diameter was 12 μm, and the particle size distribution was D10: 7 μm, D50: 12 μm, D90: 20 μm, and white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin content of 230 ppm. Met.

Example 4 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-type tris- (2, 5.6 g (3-epoxypropyl) -isocyanurate (the number T of seed crystals was 2.45 × 10 ⁸ / g) was added. Step (D): The same operation as in Example 1 was performed. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 290 g. The obtained crystal had a residual epichlorohydrin amount of 400 ppm and an epoxy value of 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
Α-tris- (2,3-epoxypropyl) -isocyanurate content of 5.0% by weight which is contained in the crystal and cannot be extracted with methanol. The average particle diameter was 18 μm, and the particle size distribution was 9 μm for D10, 18 μm for D50, and 35 μm for D90, and was white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin amount of 190 ppm. Met.

Example 5 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-tris- (2,2) having an average particle diameter of 2.7 μm as a seed crystal was used. 1.1 g of 3-epoxypropyl) -isocyanurate (the number T of seed crystals was 4.9 × 10 ⁷ / g) was added. Step (D): The same operation as in Example 1 was performed. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 280 g. The obtained crystals had a residual epichlorohydrin amount of 520 ppm and an epoxy value of 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% Of tris- (2,3-epoxypropyl) -isocyanurate which is contained in the crystal and cannot be extracted with methanol. The crystal has a melting point of 148 to 158 ° C. The average particle diameter was 27 μm, and the particle size distribution was D10 of 11 μm, D50 of 27 μm,
Was 55 μm and white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin amount of 130 ppm. Met.

Example 6 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): raising the temperature to 70 ° C. to completely dissolve the solid content
1 hour after cooling, cool to 60 ° C as seed
Β-tris- (2,3-epoxy having an average particle diameter of 2.7 μm
0.16 g of (cypropyl) -isocyanurate (seed crystal
The number T is 7 × 10 ⁶/ G). Step (D): The same operation as in Example 1 was performed. Step (E): The obtained crystal was treated with 1200 g of methanol.
And filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-type
Lis- (2,3-epoxypropyl) -isocyanurate
A crystal was obtained. The obtained crystal is a residual epic
Lorhydrin content is 640 ppm, epoxy value 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% By weight, contained in the crystal and cannot be extracted with methanol
α-type tris- (2,3-epoxypropyl) -isocyanate
The nurate content is 6.9% by weight, and the crystals have a melting point
Is 148 to 158 ° C., and the average particle size is 32 μm.
The particle size distribution was D10 11 μm, D50 32 μm, D90
Was 70 μm and white crystals. In addition, this conclusion
The crystals were rotary-dried at 130 ° C under a reduced pressure of 10 Torr in a nitrogen stream.
-Β-type obtained by drying with an evaporator for 24 hours
Lis- (2,3-epoxypropyl) -isocyanurate
Crystals have a residual epichlorohydrin content of 170 ppm
there were.

Example 7 Step (A): The same operation as in Example 1 was performed. Step (B): The solid concentration in the reaction solution becomes 25% by weight.
Epichlorohydrin at 50-60 ° C under reduced pressure
Was distilled off to obtain 6400 g of a control liquid. Step (C): raising the temperature to 53 ° C. to completely dissolve the solids
Cool to 43 ° C over 1 hour after dissolving
Β-tris- (2,3-epoxy) having an average particle diameter of 45 μm
11.2 g of (cypropyl) -isocyanurate (seed crystal
The number T is 1 × 10 ^FivePcs / g). (D) Step: After stirring at 43 ° C. for 1 hour, 4 hours up to 10 ° C.
And tris- (2,3-epoxypropyl)
-Isocyanurate crystals were precipitated and separated by filtration. Step (E): The obtained crystal was treated with 1200 g of methanol.
And filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-type
Lis- (2,3-epoxypropyl) -isocyanurate
A crystal was obtained. The obtained crystal is a residual epic
Lorhydrin content is 800 ppm, epoxy value 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% By weight, contained in the crystal and cannot be extracted with methanol
α-type tris- (2,3-epoxypropyl) -isocyanate
The nurate content is 6.8% by weight, and the crystals have a melting point
Is 148 to 158 ° C., and the average particle size is 75 μm.
The particle size distribution was D10 17 μm, D50 75 μm, D90
Was 160 μm and white crystals. Furthermore, this
The crystals were placed in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr.
Β-type obtained by drying with a reevaporator for 24 hours
Tris- (2,3-epoxypropyl) -isocyanurate
Crystalline crystals have a residual epichlorohydrin content of 170 ppm
Met.

Example 8 Step (A): The same operation as in Example 1 was performed. Step (B): A portion of epichlorohydrin was distilled off under reduced pressure at a temperature of 50 to 60 ° C. until the solid content concentration in the reaction solution became 15% by weight to obtain 10700 g of a control solution. Step (C): The temperature of the reaction system is raised to 40 ° C., and the solid content is completely dissolved, and then cooled to 30 ° C. over 1 hour.
Β-type tris- (2,3) having an average particle diameter of 45 μm as a seed crystal
-Epoxypropyl) -isocyanurate 11.2 g
(The number T of seed crystals was 1 × 10 ⁵ / g). Step (D): After stirring at 30 ° C. for 1 hour, the mixture was cooled to 0 ° C. over 4 hours to precipitate β-type tris- (2,3-epoxypropyl) -isocyanurate crystal, which was separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 260 g. The obtained crystal had a residual epichlorohydrin amount of 700 ppm and an epoxy value of 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% By weight, the content of α-type tris- (2,3-epoxypropyl) -isocyanurate which is contained in the crystal and cannot be extracted with methanol is 7.0% by weight, and this crystal has a melting point of 148 to 158 ° C. And the average particle size was 70 μm, and the particle size distribution was D10 of 15 μm, D50 of 70 μm, D90
Was 150 μm and white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin content of 180 ppm.
Met.

Example 9 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., the solid content was completely dissolved, and then cooled to 60 ° C. over 1 hour, and β-type tris- (2,3-epoxypropyl) -isocyanate was used as a seed crystal. 11.2 g of nurate (the number T of seed crystals is 1 × 10 ⁵
/ G). Step (D): Immediately at 25 ° C. without holding at the above addition temperature
After cooling for 5 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystals were precipitated and separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-type tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 270 g. The obtained crystal had a residual epichlorohydrin amount of 750 ppm and an epoxy value of 101 g /.
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% Of tris- (2,3-epoxypropyl) -isocyanurate, which is contained in the crystal and cannot be extracted with methanol, and has a melting point of 148 to 158 ° C. And the average particle size was 70 μm, and the particle size distribution was D10 of 15 μm, D50 of 70 μm, D90
Was 150 μm and white crystals. Further, the β-tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin amount of 185 ppm.
Met.

Example 10 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature was raised to 70 ° C., and after completely dissolving the solid content, the mixture was cooled to 60 ° C. over 1 hour, and β-type tris- (2,3- 11.2 g (epoxypropyl) -isocyanurate crystal was added (the number T of seed crystals was 1 × 10 ⁵ / g). Step (D): maintaining at the above addition temperature of 60 ° C. for 30 minutes, and then cooling over 2 hours to 25 ° C. to precipitate β-form tris- (2,3-epoxypropyl) -isocyanurate crystal. It was separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 275 g. The obtained crystal had a residual epichlorohydrin content of 800 ppm and an epoxy value of 101 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% Of tris- (2,3-epoxypropyl) -isocyanurate which is contained in the crystal and cannot be extracted with methanol, and has a melting point of 148 to 158 ° C. The average particle diameter was 65 μm, and the particle size distribution was D10 of 15 μm, D50 of 65 μm, D90.
Was 140 μm and white crystals. Further, the β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin amount of 165 ppm.
Met.

Example 11 Step (A): The operation was carried out in the same manner as in Example 1. (B) Step: The same operation as in Example 1 was performed. Step (C): The temperature before crystallization is 55 ° C. At this temperature, the solid component in the preparation solution is not completely dissolved, but β-tris- (2,3) having an average particle diameter of 45 μm as a seed crystal. 1.1 g of (epoxypropyl) -isocyanurate crystals
(The number T of seed crystals was 1.0 × 10 ⁴ / g). Step (D): After stirring at a temperature of 55 ° C. for 1 hour, the mixture was cooled to 25 ° C. in 4 hours to precipitate a β-type tris- (2,3-epoxypropyl) -isocyanurate crystal, which was separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 260 g. The obtained crystal had a residual epichlorohydrin amount of 700 ppm and an epoxy value of 103 g /
eq. Α-tris- (2,3) extractable with methanol
-Epoxypropyl) -isocyanurate content is 0.5
% Of tris- (2,3-epoxypropyl) -isocyanurate which is contained in the crystal and cannot be extracted with methanol, and has a melting point of 147 to 158 ° C. The average particle diameter was 50 μm, and the particle size distribution was D10: 12 μm, D50: 50 μm, D90:
Was 230 μm and white crystals. Further, β-type tris- (2,3-epoxypropyl) -isocyanurate crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours has a residual epichlorohydrin content of 220 ppm. Was.

Example 11 was repeated two more times. The physical properties of the obtained crystal are shown below.

In the second run, a yield of 265 g was obtained with β-tris-
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. This crystal has an epoxy value of 101 g / e.
q. Α-tris- (2,3-
(Epoxypropyl) -isocyanurate content 0.5% by weight, α contained in the crystal and not extractable with methanol
The type tris- (2,3-epoxypropyl) -isocyanurate content is 6.5% by weight, the crystal has a melting point of 148 to 158 ° C., an average particle size of 100 μm, and a particle size distribution of D10. 15 μm, D50 is 100 μm, D
90 was 250 μm and white crystals. Further, β obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours.
Type tris- (2,3-epoxypropyl) -isocyanurate crystals had a residual epichlorohydrin content of 190 ppm.
Met.

The third time, a yield of 260 g was obtained with β-tris-
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. This crystal has an epoxy value of 105 g / e.
q. Α-tris- (2,3-
(Epoxypropyl) -isocyanurate content 0.5% by weight, α contained in the crystal and not extractable with methanol
The tris- (2,3-epoxypropyl) -isocyanurate type content is 4.3% by weight, the crystal has a melting point of 146 to 157 ° C., an average particle size of 40 μm, and a particle size distribution of D10. 13 μm, D50 is 40 μm, D90
Was 220 μm and white crystals. Further, β obtained by drying this crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours.
Type tris- (2,3-epoxypropyl) -isocyanurate crystals have a residual epichlorohydrin content of 290 ppm.
Met.

Example 12 Step (A): The operation was carried out in the same manner as in Example 1. (B) Step: The same operation as in Example 1 was performed. Step (C): raising the temperature to 70 ° C. to completely dissolve the solid content
Allow to cool to 60 ° C for 1 hour after dissolving
Β-tris- (2,3-epoxy) having an average particle diameter of 45 μm
11.2 g of (cypropyl) -isocyanurate (seed crystal
The number T is 1 × 10 ^FivePcs / g). Step (D): stirring at 60 ° C. for 1 hour, and then 4 hours to 25 ° C.
And tris- (2,3-epoxypropyl)
-To precipitate isocyanurate crystals,
Model NS-200Ultra S manufactured by ISSEI Corporation
Apply ultrasonic waves to the solution using the Sonic Generator
Crystals were precipitated while the mixture was added and filtered. Step (E): The obtained crystal was treated with 1200 g of methanol.
And filtered. The obtained cake is dried at 80 ° C. under a reduced pressure of 5 Torr for 4 hours.
After drying, yield of 265 g of β-tris- (2,3-epoxy)
(Cipropyl) -isocyanurate crystals were obtained. Profit
The crystals obtained had an amount of residual epichlorohydrin of 40.
0 ppm, epoxy value 101 g / eq. With methanol
Extractable α-form tris- (2,3-epoxypropyl)
-0.5% by weight of isocyanurate content inside the crystal
Α-tris- (2,3
-Epoxypropyl) -isocyanurate content is 4.0.
% By weight, and this crystal has a melting point of 148 to 158 ° C.
The average particle diameter is 17 μm, and the particle size distribution is D10.
12 μm, D50 17 μm, D90 30 μm, white
It was a colored crystal. Further, the crystals were placed in a nitrogen stream at 130.degree.
2 ° C. with a rotary evaporator at 10 ° C. under a reduced pressure of 10 Torr.
Β-type tris- (2,3-epoxide obtained by drying for 4 hours
(Xypropyl) -isocyanurate crystals
Lorhydrin amount was 230 ppm.

Example 13 Step (A): Cyanur was placed 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 acid, 8328 g (90 moles) of epichlorohydrin, and 18 g of a 60% by weight aqueous solution of tetraethylammonium bromide were added to the mixture.
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.
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 dissolved and washed by adding 3600 g of water, followed by liquid separation, and further a 5% by weight aqueous sodium dihydrogen phosphate solution 1
The excess sodium hydroxide was neutralized by adding 200 g and washing, and then washed with 4800 g of water. Step (B): A portion of epichlorohydrin was distilled off under reduced pressure at a temperature of 50 to 60 ° C. until the solid concentration in the reaction solution became 40% by weight, to obtain 4000 g of a prepared solution. Step (C): The temperature was raised to 70 ° C., and after the solid content was completely dissolved, the mixture was cooled to 60 ° C. over 1 hour, and high-purity tris- (2,3- Epoxypropyl) -isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd.) was added in an amount of 36.0 g (the number T of seed crystals was 9 × 10 ⁴ / g). Step (D): After stirring at 60 ° C for 1 hour, cooling to 25 ° C in 4 hours, β-tris- (2,3-epoxypropyl)
-Isocyanurate crystals were precipitated and separated by filtration. Step (E): The obtained crystal was washed with 1200 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-form tris- (2,3-epoxypropyl) -isocyanurate crystal was obtained in a yield of 280 g. The obtained crystal had a residual epichlorohydrin content of 650 ppm and an epoxy value of 101 g.
/ Eq. Α-tris- (2,
(3-epoxypropyl) -isocyanurate content is 0.
The content of α-type tris- (2,3-epoxypropyl) -isocyanurate, which is contained in the crystal and cannot be extracted with methanol, is 6.5% by weight, and the melting point of the crystal is 148 to 158 ° C. And the average particle size was 70 μm, and the particle size distribution was D10 20 μm, D50 70 μm,
90 was 150 μm and white crystals. Further, β-crystal obtained by drying the crystal in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours.
The type tris- (2,3-epoxypropyl) -isocyanurate crystal has a residual epichlorohydrin content of 180 pp.
m.

Example 14 Step (A): The same operation as in Example 1 was performed. (B) Step: The same operation as in Example 1 was performed. Step (C): raising the temperature to 70 ° C. to completely dissolve the solid content
Allow to cool to 60 ° C for 1 hour after dissolving
Β-tris- (2,3-epoxide having an average particle diameter of 100 μm
1.1 g of (xypropyl) -isocyanurate (seed crystal
The number T is 1 × 10 ^ThreePcs / g). Step (D): stirring at 60 ° C. for 1 hour, and then 4 hours to 25 ° C.
And tris- (2,3-epoxypropyl)
-Isocyanurate crystals were precipitated and separated by filtration. Step (E): The obtained crystal was treated with 1200 g of methanol.
And filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, β-type
Lis- (2,3-epoxypropyl) -isocyanurate
A crystal was obtained. The resulting crystal is
Chlorhydrin content: 850 ppm, epoxy value: 101 g
/ Eq. Α-tris- (2,
(3-epoxypropyl) -isocyanurate content is 0.
5% by weight, contained in the crystal and cannot be extracted with methanol
Α-tris- (2,3-epoxypropyl) -isocy
The annulate content was 8.0% by weight, and this crystal was
The point is 147 to 158 ° C., and the average particle size is 110 μm.
And D10 is 40 μm and D50 is 110 μm.
m and D90 were 200 μm and white crystals. Further
Then, the crystals are reduced in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr.
Below, obtained by drying on a rotary evaporator for 24 hours
Β-tris- (2,3-epoxypropyl) -a
Socyanurate crystals have a residual epichlorohydrin content of 2
It was 00 ppm.

Comparative Example 1 Step (A): In a flask equipped with a stirrer and a thermometer, 129 g (1 mol) of cyanuric acid and epichlorohydrin 1 were added.
369 g (14.8 mol), dimethylaniline 2.0 g
In addition, the reaction was carried out by refluxing while stirring at 110 ° C. for 3.5 hours. Next, the temperature of the reaction system was cooled to 25 ° C, and 129 g of powdered sodium hydroxide was stirred.
(3.2 mol) was added while maintaining the temperature at 25 to 30 ° C., and dehydrochlorination was performed. Thereafter, the generated sodium chloride was removed by filtration, and the filtrate was washed by adding 200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate to neutralize the excess sodium hydroxide, and then washed with 600 g of water. . Step (B): A portion of epichlorohydrin was distilled off under reduced pressure at a temperature of 50 to 55 ° C. until the solid concentration in the reaction solution became 55% by weight, to obtain 480 g of a prepared solution. (D) Step: Crystallization was started at 55 ° C., cooled to 20 ° C. in 4 hours, allowed to stand at that temperature for 4 hours, and precipitated white crystals were separated by filtration. Step (E): The obtained crystals were washed with 340 g of methanol and filtered. The cake obtained is 5 ° C at 80 ° C
After drying for 4 hours under reduced pressure of rr, tris- was obtained in a yield of 84 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 2900 ppm and an epoxy value of 105 g / e.
q. Α-tris- (2,3-
Epoxypropyl) -isocyanurate content is 21% by weight, α-tris- (2,3-epoxypropyl) -isocyanurate content which is contained in the crystal and cannot be extracted with methanol is 19% by weight, and this crystal is Melting point is 12
0 to 148 ° C., the average particle diameter is 20 μm, and the particle size distribution is 2 μm for D10, 20 μm for D50, and 100 for D90.
μm, and were white crystals. Further, the crystals were dried in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours. The crystals obtained had a residual epichlorohydrin amount of 1800 ppm. Further, this crystal was obtained by melting α-tris-
The particles were partially connected to each other by (2,3-epoxypropyl) -isocyanurate to form a lump.

Comparative Example 2 Step (A): In a flask equipped with a stirrer and a thermometer, 129 g (1 mol) of cyanuric acid and epichlorohydrin 1 were added.
190 g (12.9 mol), 1.0 g of triethylamine
In addition, the reaction was carried out by refluxing at 110 to 115 ° C with stirring for 3.0 hours. Next, raise the temperature of the reaction system to 30-
The mixture was cooled to 35 ° C., and 190 g (3.4 mol) of powdered potassium hydroxide was stirred and stirred at 25 to 30 ° C. for 3 hours.
Dehydrochlorination was performed by adding an equal amount of the solution in five portions at 0 minute intervals. Thereafter, the generated potassium chloride was removed by filtration, and the filtrate was added with a 5% by weight aqueous solution of sodium hydrogen phosphate 2%.
The excess sodium hydroxide was neutralized by adding 00 g and washing, and then washed with 600 g of water. Step (B): A portion of epichlorohydrin was distilled off at a temperature of 60 to 65 ° C. and reduced pressure until the solid content in the reaction solution reached 60% by weight to obtain 440 g of a control solution. (D) Step: Crystallization was started at 65 ° C, cooled to 25 ° C in 4 hours, stirred at that temperature for 5 hours, and the precipitated white crystals were separated by filtration. Step (E): The obtained crystal was washed with 320 g of methanol and filtered. The cake obtained is 5 ° C at 80 ° C
After drying for 4 hours under reduced pressure of rr, tris was obtained in a yield of 80 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 2700 ppm and an epoxy value of 104 g / e.
q. Α-tris- (2,3-
The content of α-tris- (2,3-epoxypropyl) -isocyanurate, which is contained in the crystal and cannot be extracted with methanol, is 22% by weight, and the content of the crystal is 20% by weight. Melting point 11
8 to 148 ° C., the average particle size is 18 μm, and the particle size distribution is D10 2 μm, D50 18 μm, D90 90 μm.
m and were white crystals. The crystals were dried in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours, and the crystals obtained had a residual epichlorohydrin amount of 1700 ppm. Further, this crystal was obtained by melting α-tris-
The particles were partially connected to each other by (2,3-epoxypropyl) -isocyanurate to form a lump.

Comparative Example 3 Step (A): In a flask equipped with a stirrer and a thermometer, 129 g (1 mol) of cyanuric acid and epichlorohydrin 1 were added.
The reaction was carried out by adding 250 g (13.5 mol) of 3.0 g of a 60% by weight aqueous solution of tetraethylammonium bromide and refluxing the mixture at 110 ° C. for 3.5 hours with stirring. Next, the temperature of the reaction system was cooled to 20 to 30 ° C., and 129 g (3.2 mol) of powdered sodium hydroxide was added with stirring to remove hydrochloric acid. Thereafter, the generated sodium chloride was removed by filtration, and the filtrate was washed by adding 200 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate to neutralize the excess sodium hydroxide, and then washed with 600 g of water. . Step (B): A portion of epichlorohydrin was distilled off at a temperature of 50 to 60 ° C. and reduced pressure until the solid content concentration in the reaction solution became 50% by weight to obtain 540 g of a control solution. Step (D): Crystallization was started at 55 ° C., cooled to 25 ° C. in 4 hours, stirred at that temperature for 4.5 hours, and the precipitated white crystals were separated by filtration. Step (E): The obtained crystal was washed with 350 g of methanol and filtered. The cake obtained is 5 ° C at 80 ° C
After drying for 4 hours under reduced pressure of rr, tris- was obtained in a yield of 88 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 2200 ppm and an epoxy value of 103 g / e.
q. Α-tris- (2,3-
Epoxypropyl) -isocyanurate content is 21% by weight, α-tris- (2,3-epoxypropyl) -isocyanurate content which is contained in the crystal and cannot be extracted with methanol is 19% by weight, and this crystal is Melting point 11
8 to 148 ° C., the average particle size is 15 μm, and the particle size distribution is as follows: D10 is 2 μm, D50 is 15 μm, and D90 is 85 μm.
m and were white crystals. The crystals were dried in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours, and the crystals obtained had a residual epichlorohydrin content of 1600 ppm. Further, this crystal was obtained by melting α-tris-
The particles were partially connected to each other by (2,3-epoxypropyl) -isocyanurate to form a lump.

Comparative Example 4 Step (A): In a flask equipped with a stirrer and a thermometer, 129 g (1 mol) of cyanuric acid and epichlorohydrin 1 were added.
The reaction was carried out by adding 388 g (15.0 mol) and 3.0 g of a 60% by weight aqueous solution of tetraethylammonium bromide and refluxing the mixture at 110 ° C. for 3.5 hours. Next, the temperature of the reaction system is cooled to 40 to 50 ° C., and while stirring, 256 g of a 50% by weight aqueous sodium hydroxide solution
(3.2 mol) while maintaining the temperature at 40 to 50 ° C.
Dehydrochlorination was performed for 6 hours under reduced pressure of ６０60 Torr. Thereafter, the produced sodium chloride was washed by adding and dissolving 300 g of water, followed by liquid separation and further 5% by weight phosphoric acid 2%.
An excess amount of sodium hydroxide was neutralized by adding 100 g of an aqueous sodium hydrogen solution for washing, and then washed with 300 g of water. Step (B): A portion of epichlorohydrin was distilled off under reduced pressure at a temperature of 65 to 70 ° C. until the solid concentration in the reaction solution reached 60% by weight, to obtain 440 g of a control solution. Step (D): Crystallization was started at 70 ° C., cooled to 20 ° C. in 5 hours, allowed to stand at that temperature for 4 hours, and the precipitated white crystals were separated by filtration. Step (E): The obtained crystal was washed with 320 g of methanol and filtered. The cake obtained is 5 ° C at 80 ° C
After drying for 4 hours under reduced pressure of rr, tris was obtained in a yield of 80 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 2000 ppm and an epoxy value of 102 g / e.
q. Α-tris- (2,3-
The content of α-type tris- (2,3-epoxypropyl) -isocyanurate contained in the crystal and not extractable with methanol is 21% by weight, and the content of the crystal is 18% by weight. Melting point is 12
0 to 148 ° C., the average particle size is 18 μm, and the particle size distribution is 2 μm for D10, 18 μm for D50, and 90 μm for D90.
m and were white crystals. The crystals were dried in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr with a rotary evaporator for 24 hours, and the crystals obtained had a residual epichlorohydrin content of 1600 ppm. Further, this crystal was obtained by melting α-tris-
The particles were partially connected to each other by (2,3-epoxypropyl) -isocyanurate to form a lump.

Comparative Example 5 Step (A): The same operation as in Comparative Example 4 was performed. Step (B): A partial pressure of epichlorohydrin was distilled off at a temperature of 60 to 70 ° C. and reduced pressure until the solid content concentration in the reaction solution became 50% by weight to obtain 530 g of a control solution. Step (D): Crystallization was started at 60 ° C., cooled to 25 ° C. in 4 hours, stirred at that temperature for 4 hours, and the precipitated white crystals were separated by filtration. Step (E): The obtained crystal was washed with 280 g of methanol and filtered. The cake obtained is 5 ° C at 80 ° C
After drying for 4 hours under reduced pressure of rr, tris- was obtained in a yield of 76 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin content of 2500 ppm and an epoxy value of 102 g / e.
q. Α-tris- (2,3-
The content of α-type tris- (2,3-epoxypropyl) -isocyanurate contained in the crystal and not extractable with methanol is 14% by weight, and the content of the crystal is 18% by weight. 13 melting point
8 to 150 ° C., the average particle diameter is 16 μm, and the particle size distribution is D10 2 μm, D50 16 μm, D90 95 μm.
m and were white crystals. Further, the crystals were dried in a nitrogen stream at 130 ° C. under a reduced pressure of 10 Torr by a rotary evaporator for 24 hours. The crystals obtained had a residual epichlorohydrin amount of 1500 ppm. Further, this crystal was obtained by melting α-tris-
The particles were partially connected to each other by (2,3-epoxypropyl) -isocyanurate to form a lump.

Comparative Example 6 Step (A): The same operation as in Comparative Example 5 was performed. Step (B): The same operation as in Comparative Example 5 was performed. Step (D): The same operation as in Comparative Example 5 was performed. Step (E): The obtained crystal was filtered, washed with 280 g of methanol, added with 500 g of epichlorohydrin, heated to 70 ° C. to dissolve the crystal, and then cooled to 25 ° C. over 5 hours. The crystals were recrystallized. The crystals were washed with 250 g of methanol and dried at 80 ° C. under a reduced pressure of 5 Torr for 4 hours, and dried in β yield of 52.6 g.
(2,3-Epoxypropyl) -isocyanurate was obtained. The crystalline form has an average particle diameter of 300 μm, the residual epichlorohydrin is 2500 ppm, and α-form tris- (2,3-epoxypropyl) -isocyanurate, which is considered to be attached to the crystalline surface extractable with methanol, is 0.5% by weight and 1% by weight of α-form tris- (2,3-epoxypropyl) -isocyanurate contained in the crystal body. This crystal has a melting point of 150 to 158 ° C., an average particle diameter of 300 μm, and a particle size distribution of D10 of 100 μm, D50 of 300 μm,
D90 was 500 μm. Further, the crystal is heated to 130 ° C.
The crystals obtained by drying under reduced pressure of 10 Torr for 24 hours were found to have a residual epichlorohydrin of 2500 ppm. This means that a specific amount of α-type tris- (2,3
(Epoxypropyl) -isocyanurate was not present, and no liquid pores were formed in this crystal in the drying process at 130 ° C., so epichlorohydrin remained without being removed from this crystal. it is conceivable that.

Comparative Example 7 Step (A): The same operation as in Comparative Example 1 was performed. Step (B): The same operation as in Comparative Example 1 was performed. Step (D): The same operation as in Comparative Example 1 was performed. Step (E): The obtained crystal was washed with 1700 g of methanol and filtered. The cake obtained is 5
After drying for 4 hours under reduced pressure of Torr, tris- was obtained in a yield of 71 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 2500 ppm and an epoxy value of 104 g / e.
q. Α-tris- (2,3-
The content of epoxypropyl) -isocyanurate is 6% by weight, and the content of α-type tris- (2,3-epoxypropyl) -isocyanurate contained in the crystal and not extractable with methanol is 23% by weight. Melting point is 12
8 to 149 ° C., the average particle diameter is 20 μm, and the particle size distribution is as follows: D10 is 2 μm, D50 is 20 μm, and D90 is 100 μm.
μm, and were white crystals. In addition, this crystal
The crystal obtained by drying at 30 ° C. under a reduced pressure of 10 Torr for 24 hours has a residual epichlorohydrin content of 1700 ppm.
Met. In addition, the crystals were partly connected to each other by α-form tris- (2,3-epoxypropyl) -isocyanurate which was melted at the time of drying at 130 ° C. to form a mass.

Comparative Example 8 Step (A): The same operation as in Comparative Example 4 was performed. Step (B): The same operation as in Comparative Example 4 was performed. Step (D): The same operation as in Comparative Example 4 was performed. Step (E): The obtained crystal was washed with 1600 g of methanol and filtered. The cake obtained is 5
After drying under reduced pressure of Torr for 4 hours, tris was obtained in a yield of 66 g.
(2,3-Epoxypropyl) -isocyanurate crystals were obtained. The obtained crystals had a residual epichlorohydrin amount of 1800 ppm and an epoxy value of 102 g / e.
q. Α-tris- (2,3-
The content of α-tris- (2,3-epoxypropyl) -isocyanurate, which is contained in the crystal and is not extractable with methanol, is 21.4% by weight. The body had a melting point of 141 to 151 ° C., an average particle size of 18 μm, a particle size distribution of D10 of 2 μm, D50 of 18 μm, and D90 of 90 μm, and was white crystals. Further, the crystal obtained by drying the crystal at 130 ° C. under a reduced pressure of 10 Torr for 24 hours has a residual epichlorohydrin amount of 1500 p.
pm. In addition, the crystals were partly connected to each other by α-form tris- (2,3-epoxypropyl) -isocyanurate which was melted at the time of drying at 130 ° C. to form a mass.

In Examples 2 to 4, a large number of seed crystals were added. In Example 12, ultrasonic waves were applied during crystallization.
In these examples, the average particle diameter of the obtained crystals was small, and these were found to remain even after drying alone at about 80 ° C.
-The amount of isocyanurate is small. It is considered that epichlorohydrin and α-type tris- (2,3-epoxypropyl) -isocyanurate are removed during the crystallization process and the washing process due to the large specific surface area. These fine particles are considered to have a small amount of epichlorohydrin and α-type tris- (2,3-epoxypropyl) -isocyanurate incorporated into the crystal because the formation speed of the particles proceeds slowly.

In Examples 1, 5 to 11, and 13 to 15, even if the particles have a residual epichlorohydrin of about 400 to 900 ppm when dried at 80 ° C., the α-type tris- (2,3) -Epoxypropyl)
Α-type tris- (2,3-epoxypropyl) -isocyanurate formed in the pores at a drying temperature of about 130 ° C. by the isocyanurate forms liquid pores, and epichlorohydrin passes through the pores. The amount of residual epichlorohydrin present in the final particles to be considered to be removed is less than 300 ppm.
Further, since the content of the melted α-type tris- (2,3-epoxypropyl) -isocyanurate is 2 to 15% by weight, it hardly oozes out of the crystal, so that the agglomeration phenomenon hardly occurs.

Since the crystals obtained in Comparative Examples 1 to 5 do not use the method of the present invention using seed crystals, even if they are gradually cooled in the cooling process, rapid crystallization occurs with a slight temperature change, A large amount of epichlorohydrin or α-tris- (2,3
-Epoxypropyl) -isocyanurate results in reduced purity of the resulting crystals. If the amount of the α-form in the crystal exceeds 15% by weight, the amount of the α-form which is melted in the drying process at about 130 ° C. becomes large, and the crystal itself cannot maintain the particle state, and the melted α-form Agglomeration phenomenon of particles easily occurs.

Also, a large amount of α-form exists outside the crystal,
Even if it is washed with 4 times (by weight) or more methanol than tris- (2,3-epoxypropyl) -isocyanurate, it cannot be efficiently removed. This large amount of the α-form also dissolves in the drying step at about 130 ° C., causing the action of the binder, and the particles are fused to each other to cause agglomeration.

When this agglomeration phenomenon occurs, in the production of β-form tris- (2,3-epoxypropyl) -isocyanurate crystal, the product becomes a large lump on the drying line in the step (E) and the production line Is not preferable because it may stop the operation.

[0085]

According to the present invention, the β-form tris- (2,3-epoxypropyl) -isocyanurate crystal containing the α-form tris- (2,3-epoxypropyl) -isocyanurate inside the crystal is: Since it is obtained by the operation of adding a seed crystal to the reaction solution obtained in the step A), it can be easily produced even in industrial scale production.

This crystal is composed of α-tris-
Low epichlorohydrin content due to (2,3-epoxypropyl) -isocyanurate. The α-type tris- (2,3-epoxypropyl) -isocyanurate present inside the pores of the crystal melts and becomes liquid when dried at about 130 ° C., and epichlorohydrin is released outside the crystal through these pores. But the liquid α inside the crystal
The type tris- (2,3-epoxypropyl) -isocyanurate does not ooze out of the crystal when heated at about 130 ° C., so that the agglomeration of particles is unlikely to occur. The α-type tris- (2,3-epoxypropyl) -isocyanurate in the crystal is not eluted out of the crystal even by the solvent.

The β-type tris obtained by the present invention
The (2,3-epoxypropyl) -isocyanurate crystal is an α-type tris- (2,3-
(Epoxypropyl) -isocyanurate and epichlorohydrin, which are harmful to humans and electronic materials, are low and highly purified.
Used in the field of thermosetting resist inks.

Continued on the front page (72) Inventor Motohiko Hidaka 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Industry Co., Ltd. Central Research Laboratory (72) Inventor Atsumi Aoki 6901-1, Onoda, Onoda-shi, Yamaguchi Nissan Chemical Industry Co., Ltd. Onoda factory

Claims (11)

[Claims] 1. A β-type tris- (2,3-epoxypropyl) -isocyanurate containing α-type tris- (2,3-epoxypropyl) -isocyanurate at a ratio of 2 to 15% by weight in a crystal. Crystal. 2. The crystalline material has an average particle size of 10 to 500 μm.
The β-form tris- (2,3-epoxypropyl) -isocyanurate crystal according to claim 1, which is: 3. The following steps (A), (B), (C), (D) and (E): Step (A): reacting 1 mol of cyanuric acid with 5-180 mol of epichlorohydrin to react with cyanuric acid A reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate by producing an epichlorohydrin adduct of the following, followed by dehydrochlorination, Step (B): obtained in Step (A) Tris- (2,3-
A step of preparing a reaction solution containing (epoxypropyl) -isocyanurate to a solid content concentration of 10 to 50% by weight; step (C): the liquid obtained in step (B) is a saturated solution (C) a step of adding a seed crystal at a temperature 5 to 20 ° C. lower than the temperature at which the liquid is formed.
α-type tris- (2, a step of slowly cooling at a cooling rate within hr to obtain a crystal by filtration, and a step of washing and drying the crystal obtained in the step (E): (D). A method for producing a β-type tris- (2,3-epoxypropyl) -isocyanurate crystal in which 3-epoxypropyl) -isocyanurate is contained in the crystal at a ratio of 2 to 15% by weight. 4. The process (A) comprises: (a) 1 mol of cyanuric acid, (b) 5 to 180 mol of epichlorohydrin, and (c) a tertiary amine, a quaternary ammonium salt or a quaternary ammonium base as a catalyst. , A tri-substituted phosphine, and a reaction solution obtained by reacting 0.001 to 0.1 mol of at least one compound selected from the group consisting of quaternary phosphonium salts, with an alkali metal hydroxide or After adding 2 to 6 mol of an alkali metal alcoholate and dehydrochlorinating,
The production method according to claim 3, which is a step of obtaining a reaction solution containing tris- (2,3-epoxypropyl) -isocyanurate by removing an alkali metal salt. 5. The step (C) comprises raising the temperature of the liquid obtained in the step (B) to a temperature higher than the temperature at which a saturated solution is formed, and then lowering the temperature to 5-20 ° C. lower than the temperature at which the saturated solution is formed. 5. A step of adding a seed crystal after cooling.
The production method described in 1. 6. The addition of a seed crystal in the step (C) depends on the following formulas (1) and (2): 1 × 10 ¹⁰ ≧ T ≧ 1 × 10 ² Formula (1) 1.4 × 10 ¹² (m / (M × D ³ )) Formula (2) [where T is the number of seed crystals added per weight of tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution] The number (pieces / g), m is the weight of the seed crystal added (g), D is the average particle diameter of the seed crystal, 2 to 300 μm, and M is tris- (2,3-epoxypropyl) -isocyanurate in the reaction solution. Weight (g). Claims 3 to 5 that satisfy
The production method according to any one of the above. 7. The seed crystal added in the step (C) is β-type tris- (2,3-epoxypropyl) -isocyanurate or β-type tris- (2,3-epoxypropyl)-
The method according to any one of claims 3 to 6, which is a mixture of isocyanurate and α-type tris- (2,3-epoxypropyl) -isocyanurate. 8. In the step (D) of slowly cooling the liquid material,
The method according to any one of claims 3 to 7, wherein ultrasonic waves are applied to the liquid material. 9. The washing of the step (E) is performed by using α-tris-
Having a solubility of 0.5 g / 100 g or more in (2,3-epoxypropyl) -isocyanurate at 20 ° C.,
And a solvent having a solubility of less than 0.5 g / 100 g in β-tris- (2,3-epoxypropyl) -isocyanurate at 20 ° C. is added to β-tris- (2,3-epoxypropyl) -isocyanurate. 0. for crystal.
The method according to any one of claims 3 to 8, wherein the method is used in an amount of 5 to 10 times by weight. 10. The crystal obtained in the step (D) has an average particle diameter of 20 to 500 μm, and in the step (E), is dried at a temperature of 120 to 140 ° C. in an air stream under normal pressure or reduced pressure. The method according to any one of claims 3 to 9, which is performed. 11. The crystal obtained in the step (D) has an average particle size of 10 to 20 μm, and in the step (E), is dried at a temperature of 40 to 120 ° C. in an air stream under normal pressure or reduced pressure. The method according to any one of claims 3 to 9, which is performed.