TWI453214B - Sucrose benzoate composition and sucrose benzoate composition - Google Patents

Description

Method for producing sucrose benzoate composition and sucrose benzoate composition

The present invention relates to a method for producing a sucrose benzoate composition and a sucrose benzoate composition. Specifically, the present invention relates to a method for producing a sucrose benzoate composition and a sucrose benzoate composition, wherein the sucrose benzoate composition is less colored upon heating.

In the past, sucrose benzoate has been used as a plasticizer or dispersant for various industrial applications. Specifically, sucrose benzoate is known as a film forming material for use as a specular gloss nail material (Patent Document 1). . Further, in recent years, sucrose benzoate has also been used as a resin additive such as an image-receiving sheet for thermal transfer (Patent Document 2). In the manufacturing steps in such applications, sucrose benzoate has a problem of coloring due to heating, and particularly, when the average degree of esterification is low, coloring is remarkable.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-89389

Patent Document 2: Japanese Patent Laid-Open No. Hei 6-255274

The present invention has been made in view of the above actual circumstances, and aims to provide a A method for producing a sucrose benzoate composition and a sucrose benzoate composition, the sucrose benzoate composition is not colored even when heated.

The present inventors have repeatedly made efforts to carry out research and found out that the present invention has been completed: by formulating a carboxylate in sucrose benzoate, a sucrose benzoate composition can be obtained, even if heated. Will color.

In other words, the first gist of the present invention is a sucrose benzoate composition which is prepared by formulating a carboxylate in sucrose benzoate. In the sucrose benzoate composition, the carboxylate is preferably 0.001% by weight or more and 1% by weight or less based on the sucrose benzoate. In addition, it is preferred that the carboxylate is one or more selected from the group consisting of a saturated carboxylic acid salt, an unsaturated carboxylic acid salt, a hydroxy acid salt, and a polycarboxylic acid salt. Further, the carboxylate is preferably an alkali metal salt of a polyvalent carboxylic acid of 2 or more. Further, it is preferred that the average degree of esterification of the sucrose benzoate is 6.5 or less. A second aspect of the present invention is a process for producing a sucrose benzoate composition, which is a process for producing a sucrose benzoate composition, which comprises the steps of: sucrose benzoate and a carboxylate a step of dissolving in an organic solvent and/or water; and a step of removing the organic solvent and/or water from the mixed solution.

[Preferred form of implementing the invention]

Next, an embodiment of the present invention will be described.

The composition of the present invention is characterized in that a carboxylate is formulated in sucrose benzoate. Sucrose benzoate is generally produced by esterification of sucrose with benzamidine chloride. Since sucrose has 8 hydroxyl groups, sucrose benzoate having an average degree of esterification of more than 0 and 8 or less is present. . The average degree of esterification of the sucrose benzoate used in the composition of the present invention is not particularly limited, and any of the above average esterification degrees of sucrose benzoate can be used.

In the case of coloring by heating, the average degree of esterification is particularly remarkable when the average degree of esterification is low. Therefore, in the present invention, the average degree of esterification of sucrose benzoate is preferably 6.5 or less, and preferably 5.7 or less.

The method for producing sucrose benzoate used in the present invention is known, and can be produced by the production method described in JP-A-52-95625. In addition, a commercially available sucrose benzoate can be used, and specifically, "MONOPET SB" (registered trademark) manufactured by Daiichi Kogyo Co., Ltd. can be used.

The carboxylate used in the present invention is not particularly limited, and a salt formed of a carboxylic acid and an alkali metal or an alkaline earth metal is preferred. The carboxylic acid is a saturated carboxylic acid, an unsaturated carboxylic acid, a hydroxy acid or a polycarboxylic acid. Wait. A carboxylic acid other than these, such as an aromatic carboxylic acid, tends to have a coloring prevention effect.

Specific examples of the carboxylic acid include a formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, lauric acid, myristic acid, and the like. Palmitic acid, heptadecanoic acid, stearic acid, and the like. Examples of the unsaturated carboxylic acid include oleic acid, linoleic acid, linoleic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid and the like. The hydroxy acid may, for example, be lactic acid, malic acid, citric acid or the like. Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, and hydrochloric acid. Gluconic acid and so on. Among the above carboxylates, a particularly preferred carboxylate is a carboxylate composed of a hydroxy acid and/or a polycarboxylic acid and an alkali metal. Specifically, the hydroxy acid is particularly preferred as malic acid and citric acid, and the polycarboxylic acid is particularly preferred as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and gluconic acid. The metal in the aforementioned carboxylate is particularly preferred as the alkali metal. When a polyvalent metal such as an alkaline earth metal is blended, the sucrose benzoate composition may be turbid.

In the present invention, the amount of the carboxylate to be added to the sucrose benzoate is not particularly limited, and is preferably 0.001% by weight or more and 1% by weight or less, and more preferably 0.01% by weight or more and 0.1% by weight or less. If the amount is less than 0.001% by weight, the coloring prevention performance may be insufficient, and when it exceeds 1% by weight, the transparent sucrose benzoate may not be easily obtained.

In the present invention, the method for producing the sucrose benzoate composition is not particularly limited, and there is a production method in which sucrose benzoate is mixed with a carboxylate in a powder state, and the organic solvent is dissolved in the organic solvent. a method of solvent and/or water; mixing the carboxylic acid salt with a sucrose benzoic acid which is molten or dissolved in an organic solvent and/or water after being maintained in a powder state or dissolved in an organic solvent and/or water. The method in the ester. When an organic solvent and/or water is used in the aforementioned production method, the solvent is appropriately removed by heating or reduced pressure.

The production method of the present invention is preferably a method in which an organic solvent and/or water is removed from the mixed solution by dissolving and mixing the sucrose benzoate with the carboxylate in an organic solvent and/or water. A method of dissolving and mixing sucrose benzoate and a carboxylate in an organic solvent and/or water, for example, mixing sucrose benzoate with a carboxylate in a powder state, and dissolving the sucrose benzoate a method of mixing organic solvents and/or water; dissolving a carboxylate in an organic solvent and/or water a method of mixing it in a molten sucrose benzoate to form a mixture; a method of directly adding a carboxylate to a sucrose benzoate dissolved in an organic solvent and/or water; After the salt is dissolved in an organic solvent and/or water, it is added to a method of mixing in an sucrose benzoate dissolved in an organic solvent and/or water. The method of removing the organic solvent and/or water is not particularly limited, and it is usually carried out under heating and reduced pressure. The heating and depressurization conditions can be appropriately set, and are usually 90 to 200 ° C, and the decompression conditions are 1 to 200 mmHg.

In the method for producing a sucrose benzoate composition of the present invention, it is more preferred that after the esterification reaction in the sucrose benzoate production step is completed and the organic solvent is derived from sucrose benzoate and organic Before the mixture of the solvent mixture is removed, the carboxylate is added to the mixture after maintaining the powder or dissolved in an organic solvent and/or water. The removal of the organic solvent can usually be carried out under the same heating and reduced pressure conditions as described above. By adding the carboxylate before the removal of the organic solvent, it is possible to prevent coloring by heating, and the subsequent purification step can be easily performed.

The organic solvent is not particularly limited, and examples thereof include benzene, toluene, xylene, ethylbenzene, chlorobenzene, chlorotoluene, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, diethyl ether, and diisopropyl. Ether, acetone, methyl ethyl ketone, cyclohexanone, two Dioxane, tetrahydrofuran, methyl acetate, tertiary butanol, and the like.

In the composition of the present invention, other additives can be blended in a range that does not hinder the effect. Specific examples thereof include various antioxidants and preservatives such as dibutylhydroxytoluene and pentaerythritol 肆[3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate]. The amount of such blending is not particularly limited and can It is added within the range not impairing the effects of the present invention.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited by the examples. In the examples and comparative examples, the parts and % are based on weight unless otherwise specified.

<Modulation of sucrose benzoate>

Using a commercially available sucrose benzoate (product name: MONOPET SB (registered trademark), manufactured by Dai-Il Pharmaceutical Co., Ltd.), the high esterification degree sucrose benzoate was removed by a column to obtain an average Sucrose benzoate having a degree of esterification of 5.7.

<1. Evaluation of the color of the formulation (1)>

After melting the sucrose benzoate (APHA (American Public Health Association) chromaticity <10) at 120 ° C, various amounts described in Table 1 shown in Table 1 below were quickly added. Carboxylate. This sucrose benzoate composition was continuously heated at 120 ° C for 16 hours. After the heat treatment, after re-dissolving in toluene to become 50%, the hue and appearance were evaluated on the basis of the following criteria. The evaluation results are shown in Table 1 below.

<Hue evaluation benchmark>

◎: APHA color is less than 20

○: APHA chromaticity is 20 or more and 50 or less

×: APHA chromaticity exceeds 50

<Appearance evaluation>

The transparency (transparent or slightly turbid) is judged by the naked eye.

As shown in Table 1, in the case of sucrose benzoate obtained by melt mixing, when various carboxylates were not added, the hue was deteriorated by heating (Comparative Example 1), but various carboxylic acids were added. In Examples 1 to 4 of the salt, the hue does not change.

<2. Evaluation of the color of the formulation (2)>

The various carboxylates described in Table 2 in the amounts shown in Table 2 were added as a 10% aqueous solution to a 50% toluene solution of sucrose benzoate (average degree of esterification 5.5) (APHA color < After 10), the solvent was removed at 130 ° C and 15 mmHg or less, and the amount of residual toluene was 0.1% or less. After the obtained sucrose benzoate was again dissolved in toluene to become 50%, the hue and appearance were evaluated on the basis of the above criteria. The evaluation results are shown in Table 2.

As shown in Table 2, it is prepared by a method of dissolving in an organic solvent and water. In the case of the sucrose benzoate, when the various carboxylates were not added, the hue deteriorated by heating (Comparative Example 2), but Examples 5 to 10 in which various carboxylates were added did not change the hue.

<3. Color evaluation when recovering organic solvents> [Manufacture of sucrose benzoate]

In a 1 L five-necked flask equipped with a stirring bar, a thermometer, a condenser, a dropping funnel, and a pH electrode connected to a pH meter, 34.2 parts of sucrose and 70 parts of water were fed and dissolved, and then cooled to 10 in a water bath. Below °C, 100 parts of cyclohexanone containing 80 parts of benzamidine chloride was slowly added and uniformly dissolved. While maintaining the temperature at 20 ° C or lower, 48.5 parts of a 48% aqueous sodium hydroxide solution was added from the dropping funnel while maintaining the pH at 10 to 11. The drip is usually completed within 1 hour. Then, the water bath was removed, and after stirring at room temperature of 20 to 30 ° C for 1 hour to complete the reaction, the reaction was terminated. Then, a certain amount of sodium carbonate was added and heated to convert a trace amount of residual benzamidine chloride to sodium benzoate.

[Coloring evaluation]

The various carboxylates described in Table 3 in the amounts shown in Table 3 below were added to the reaction mixture as a 10% aqueous solution, and then the solvent was removed at 150 ° C under reduced pressure (5 mmHg). And it is completed when the residual solvent (cyclohexanone) becomes 0.05% or less. After the obtained sucrose benzoate was again dissolved in toluene to become 50%, the hue and appearance were evaluated on the basis of the above criteria. The evaluation results are shown in Table 3.

As shown in Table 3, in the method for producing a carboxylate salt when a solvent is recovered in the production step of sucrose benzoate, when various carboxylate salts are not added, the hue is deteriorated by heating (Comparative Example 3), but Examples 11 to 14 in which various carboxylates were added did not change the hue.

The sucrose benzoate composition of the present invention can be used as a plasticizer or a dispersant for various industrial applications, and specifically, it can be used as a film forming material for a specular gloss nail material, an image receiving sheet for thermal transfer printing, or the like. The resin additive is used.

The present invention has been described in detail above with reference to the specific embodiments of the present invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. Obviously known.

The present application is based on Japanese Patent Application No. 2011-136058, filed on Jun.

Claims (6)

A sucrose benzoate composition obtained by formulating a carboxylate in sucrose benzoate, and an average degree of esterification of the sucrose benzoate is 6.5 or less. The sucrose benzoate composition according to claim 1, wherein the carboxylic acid salt is 0.001% by weight or more and 1% by weight or less based on the sucrose benzoate. The sucrose benzoate composition according to claim 1, wherein the carboxylic acid salt is one or two selected from the group consisting of a saturated carboxylic acid salt, an unsaturated carboxylic acid salt, a hydroxy acid salt and a polycarboxylic acid salt. More than one species. The sucrose benzoate composition according to claim 2, wherein the carboxylic acid salt is one or two selected from the group consisting of a saturated carboxylic acid salt, an unsaturated carboxylic acid salt, a hydroxy acid salt and a polycarboxylic acid salt. More than one species. The sucrose benzoate composition according to any one of claims 1 to 4, wherein the carboxylic acid salt is an alkali metal salt of a polyvalent carboxylic acid of 2 or more. A method for producing a sucrose benzoate composition, which is a method for producing the sucrose benzoate composition according to any one of claims 1 to 5, which comprises the steps of: sucrose benzoate a step of dissolving and mixing the carboxylate in an organic solvent and/or water; and removing the organic solvent and/or water from the mixed solution.