JP5814034B2 - Hydroxyalkyl cellulose composition - Google Patents

Description

  The present invention relates to a hydroxyalkyl cellulose composition used for various uses such as thickeners such as paints and cosmetics, stabilizers for emulsion polymerization, binders for pharmaceutical tablets, film coating materials and the like.

  Hydroxyalkyl cellulose is used in various applications such as thickeners for paints and cosmetics, stabilizers for emulsion polymerization, binders for pharmaceutical tablets, film coating materials, and the like.

  When hydroxyalkyl cellulose is used for the above-mentioned use, for example, hydroxyalkyl cellulose is dissolved in water or the like. However, since hydroxyalkyl cellulose has high water solubility, when the particles are put into water, the surface of the particles immediately gels, and the gelled material aggregates (mamasko phenomenon), so that an undissolved product tends to remain.

  In order to prevent this mamako phenomenon, a method in which a water-soluble polymer containing a hydroxyl group pretreated with aldehyde (glyoxal) is added to water or swollen with water, and then the pH of the solution is changed to an alkaline range. Is known (see Patent Document 1).

  In addition, as a system that does not use glyoxal, a method for preventing mamako is known by using an agglomerated hydroxyethyl cellulose composition containing a particulate hydroxyethyl cellulose and a low molecular weight hydroxyethyl cellulose composition ( Patent Document 2).

  On the other hand, it is known that by adding a fatty acid (R-COOH) to a water-soluble polymer compound powder, the prevention of agglomeration due to moisture absorption and the water dispersibility during water dissolution are improved (see Patent Document 3). ).

Japanese Patent Publication No.42-6664 Special table 2010-515735 gazette JP-A-55-127447

  Glyoxal disclosed in Patent Document 1 is recognized as having strong mutagenicity according to the classification of existing chemical substance inspection mutagenicity of the Industrial Safety and Health Law. In addition, the Chemical Substance Emission Control Management Promotion Act (PRTR Law) falls under the category of first-class designated chemical substances, and there are concerns about safety and environmental issues for the human body. Further, there are problems such as requiring pH adjustment and yellowing due to heat in the drying process in order to prevent mamako.

  In the method disclosed in Patent Document 2, the dissolution rate is slow, and there is a problem in the macho prevention effect when using high-viscosity hydroxyethyl cellulose.

  On the other hand, the fatty acid (R-COOH) addition system disclosed in Patent Document 3 achieves some anti-maco performance, but phenomena such as a decrease in the transparency of the aqueous solution and an increase in viscosity are observed, and the performance of the product is observed. There is a problem in terms.

  The subject of this invention is providing the hydroxyalkyl cellulose composition which is excellent in the dispersibility and solubility to water, and the transparency of aqueous solution is high.

  As a result of intensive studies to solve the above problems, the present inventor has a hydroxyalkyl cellulose composition containing a specific amount of a fatty acid ester with respect to hydroxyalkyl cellulose, which is excellent in dispersibility and solubility in water. And it discovered that the transparency of aqueous solution was high, and came to complete this invention.

The present invention is a hydroxyalkyl cellulose composition containing 0.1 to 5 parts by mass of a fatty acid ester with respect to 100 parts by mass of a hydroxyalkyl cellulose , wherein the fatty acid ester is a saturated or unsaturated fatty acid having 4 to 30 carbon atoms. The present invention relates to a hydroxyalkyl cellulose composition, which is an ester of a monohydric alcohol having 1 to 22 carbon atoms .

  The hydroxyalkyl cellulose composition of the present invention has excellent dispersibility in water, so there is no generation of mako at the time of dissolution, and good solubility leads to shortening of the dissolution time, and excellent transparency when made into an aqueous solution. It has an excellent effect of exhibiting sex.

  The hydroxyalkyl cellulose composition of the present invention contains a hydroxyalkyl cellulose and a fatty acid ester.

  Examples of the hydroxyalkyl cellulose in the present invention include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose and the like. Among these, hydroxyethyl cellulose is preferable from the viewpoint of excellent thickening properties.

  Hydroxyalkyl cellulose is obtained by reacting alkali cellulose obtained by treating cellulose with an alkaline aqueous solution with alkylene oxide in a reaction solvent.

  Examples of cellulose include sheet-like and powdery cotton linters, wood pulp, and the like. Although it does not specifically limit as aqueous alkali solution, For example, the aqueous solution of alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are mentioned. In these, since it is cheap, the aqueous solution of sodium hydroxide is preferable. Although the density | concentration of aqueous alkali solution is not specifically limited, About 10-30 mass% is preferable normally. From the viewpoint of improving the fluidity of the slurry, avoiding the local progress of the reaction between the cellulose and the alkali, and improving the volumetric efficiency, the amount of the alkaline aqueous solution used in producing the alkali cellulose is 100% cellulose. It is desirable that it is 1000 to 6000 parts by mass, preferably 2000 to 5000 parts by mass with respect to parts by mass.

  Examples of the method for treating cellulose with an alkaline aqueous solution include methods such as immersion and mixing. More specifically, cellulose is immersed in an alkaline aqueous solution, and usually mixed for 20 minutes to 2 hours at 20 to 50 ° C. in a container equipped with a stirring blade. And a method of squeezing and removing the alkaline aqueous solution.

  Next, a crude hydroxyalkyl cellulose can be obtained by reacting the obtained alkali cellulose with an alkylene oxide in a reaction solvent.

  Examples of the alkylene oxide include alkylene oxides having 2 to 6 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide. Among these, ethylene oxide is preferable from the viewpoint of easy reaction with alkali cellulose.

  The amount of the alkylene oxide used is determined according to the number of added moles of the target alkyl group. For example, when ethylene oxide is used as the alkylene oxide, the amount of ethylene oxide used is increased from the viewpoint of increasing the amount of addition to cellulose, increasing the solubility of hydroxyalkyl cellulose, and increasing the yield of hydroxyalkyl cellulose. 60-200 mass parts is preferable with respect to mass parts, and 80-180 mass parts is more preferable.

  Although it does not specifically limit as reaction solvent, For example, Alcohols, such as isopropyl alcohol, isobutyl alcohol, tert-butyl alcohol, and isoamyl alcohol; Ethers, such as a dioxane and 1, 2- dimethoxyethane; Acetone, methyl ethyl ketone, methyl isobutyl ketone And ketones.

  The use amount of the reaction solvent is preferably 20 to 800 parts by mass with respect to 100 parts by mass of alkali cellulose, from the viewpoint of avoiding that alkylene oxide is locally added to cellulose and increasing the volumetric efficiency, and 20 to 600 parts by mass. Part by mass is more preferable.

  The reaction temperature is usually preferably 30 to 80 ° C. from the viewpoint of shortening the reaction time by promoting the reaction and avoiding the rapid progress of the reaction and facilitating the control of temperature and pressure. ~ 60 ° C is more preferred.

  The reaction time varies depending on the reaction temperature and cannot be determined unconditionally, but is usually preferably about 1 to 5 hours.

  The hydroxyalkyl cellulose obtained after completion of the reaction may be subjected to neutralization granulation treatment using a neutralizing agent, followed by drying and pulverization under normal pressure or reduced pressure. The neutralizing agent is not particularly limited, and examples thereof include inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; organic acids such as formic acid, acetic acid and propionic acid. In these, an excess acid can be easily removed from the obtained hydroxyalkyl cellulose, and an organic acid is preferable and an acetic acid is more preferable from a viewpoint with little toxicity.

  Moreover, before neutralization granulation treatment, the mixed solution is added to the hydroxyalkyl cellulose and washed to obtain a hydroxyalkyl cellulose such as surplus alkali metal hydroxide, alkylene oxide, and alkylene glycols by-produced from both. Other impurities may be removed.

  Although it does not specifically limit as a mixed solution used for washing | cleaning, From a viewpoint which can remove the excess alkali and the salt produced | generated by neutralization efficiently, a hydrophilic solvent and water are used for the water-soluble organic solvent used by reaction. The mixed solvent added is preferable. Specific examples of the mixed solvent include isopropyl alcohol / methanol / water, isobutyl alcohol / methanol / water, tert-butyl alcohol / methanol / water, acetone / methanol / water, methyl butyl ketone / methanol / water, methyl isobutyl ketone / methanol. / Water, methyl isobutyl ketone / isopropyl alcohol / water, methyl isobutyl ketone / tert-butyl alcohol / water, and the like. Among these, a mixed solution in which methanol and water are added to the reaction solvent used during the reaction is preferable from the viewpoint of high washing efficiency and easy distillation recovery of the solvent. The amount of methanol at this time is preferably about 20 to 60% by weight in the total amount of the mixed solution, and the amount of water is usually preferably about 5 to 30% by weight in the total amount of the mixed solution.

  The amount of the mixed solution used was used as a raw material in the production of alkali cellulose for the purpose of avoiding that washing was not performed sufficiently, avoiding the effect that was not suitable for the amount used, and becoming uneconomical. Usually, about 500 to 6000 parts by mass is preferable with respect to 100 parts by mass of cellulose, and more preferably 1000 to 4000 parts by mass. Such a cleaning process may be performed at least once.

  Furthermore, you may dry and grind | pulverize the isolated hydroxyalkyl cellulose as needed under normal pressure or pressure reduction.

  The fatty acid ester in the present invention is preferably an ester of a saturated or unsaturated fatty acid having 4 to 30 carbon atoms and a monohydric alcohol having 1 to 22 carbon atoms.

  Specific examples of saturated fatty acids include caproic acid, enanthic acid, caprylic acid, octylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, tuberculostearic acid Arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid and the like.

  Specific examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, pinolenic acid, eleostearic acid, stearidonic acid, boseopentaenoic acid, gadoleic acid , Eicosenoic acid, eicosadienoic acid, mead acid, eicosatrienoic acid, arachidonic acid, eicosatetraenoic acid, eicosapentaenoic acid, erucic acid, adrenic acid, ozbondic acid, succinic acid, docosahexaenoic acid, nervonic acid, tetracopentaene Acid, herring acid and natural fat fatty acids such as olive oil fatty acid, rapeseed oil fatty acid, palm oil fatty acid, ben flower oil fatty acid, linseed oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, sesame oil fatty acid, perilla oil fatty acid, Kiri oil fatty acid, castor oil Acid and the like.

  As monohydric alcohols having 1 to 22 carbon atoms, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, ethylhexyl alcohol, nonyl alcohol, decyl alcohol , Undecyl alcohol, dodecyl alcohol, isododecyl alcohol, tridecyl alcohol, isotridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, isocetyl alcohol, hexyldecyl alcohol, heptadecyl alcohol, octadecyl alcohol, isostearyl alcohol , Cetearyl alcohol, oleyl alcohol, nonadecyl alcohol, ara Alcohol, octyldodecyl alcohol, behenyl alcohol, and the like.

  Specific examples of fatty acid esters include ethyl caproate, ethyl caprylate, cetyl caprylate, octadecyl caprylate, ethyl caprate, isopropyl laurate, hexyl laurate, dodecyl laurate, isostearyl laurate, cetyl laurate, lauryl Isocetyl acid, butyl myristate, isopropyl myristate, decyl myristate, isotridecyl myristate, tetradecyl myristate, cetyl myristate, isocetyl myristate, isostearyl myristate, octyldodecyl myristate, ethyl palmitate, isopropyl palmitate, palmitate Octyl acid, dodecyl palmitate, ethylhexyl palmitate, cetyl palmitate, hexyldecyl palmitate, octadecyl palmitate , Isostearyl palmitate, ethyl stearate, isopropyl stearate, butyl stearate, isobutyl stearate, octyl stearate, ethyl hexyl stearate, tridecyl stearate, cetyl stearate, isocetyl stearate, cetearyl stearate, octadecyl stearate Octyldodecyl stearate, ethyl isostearate, hexyl isostearate, tridecyl isostearate, isostearyl isostearate, octyldodecyl isostearate, ethyl crotonate, methyl oleate, ethyl oleate, octyl oleate, dodecyl oleate, oleic acid Isododecyl, oleyl oleate, octyldodecyl oleate, ethyl linoleate, isoprene linoleate Pills, oleyl linoleate, ethyl linolenate, coconut oil fatty acid ethyl and the like.

  Among these, the hydroxyalkyl cellulose composition obtained is excellent in dispersibility in water, the dissolution rate is fast, and the transparency is also high, from the viewpoint of ethyl caproate, ethyl caprylate, ethyl caprate, isopropyl myristate, Ethyl stearate, isopropyl stearate, octyl stearate, ethyl hexyl stearate, octadecyl stearate, ethyl isostearate, tridecyl isostearate, ethyl crotonate, methyl oleate, ethyl oleate, octyl oleate, dodecyl oleate, oleic acid Preferred is at least one selected from the group consisting of octyldodecyl, oleyl oleate, ethyl linoleate, isopropyl linoleate, oleyl linoleate, ethyl linolenate and ethyl coconut fatty acid, Prong ethyl, ethyl caprylate, ethyl caprate, at least one selected from the group consisting of ethyl crotonate and ethyl oleate are more preferred. These fatty acid esters may be used alone or in combination of two or more.

  The usage-amount of fatty acid ester is 0.1-5 mass parts with respect to 100 mass parts of hydroxyalkyl cellulose, Preferably, it is 0.2-4 mass parts. When the amount used is less than 0.1 parts by mass, the dispersibility of the resulting hydroxyalkyl cellulose composition in water becomes poor. When the amount used exceeds 5 parts by mass, the transparency of the aqueous solution using the resulting hydroxyalkyl cellulose composition becomes poor.

  There is no limitation in particular in the manufacturing method of the hydroxyalkyl cellulose composition of this invention. The hydroxyalkyl cellulose composition of the present invention can be prepared, for example, by a method in which a solution in which a fatty acid ester is dissolved in a solvent is added to the hydroxyalkyl cellulose. More specifically, in the step of producing hydroxyalkyl cellulose, it is preferable to add a solution in which a fatty acid ester is dissolved in a solvent before or after the drying step.

  The solvent for dissolving the fatty acid ester is not particularly limited. From the viewpoint of uniform dispersion on the surface of the hydroxyalkyl cellulose particles, the solvent for dissolving the fatty acid ester is a water-soluble solvent used in the reaction of adding alkylene oxide to alkali cellulose. A mixed solvent obtained by adding a hydrophilic solvent to an organic solvent is preferable. Specific examples of the mixed solvent include isopropyl alcohol / methanol, isobutyl alcohol / methanol, tert-butyl alcohol / methanol, acetone / methanol, methyl butyl ketone / methanol, methyl isobutyl ketone / methanol, methyl isobutyl ketone / isopropyl alcohol, methyl isobutyl. And ketone / tert-butyl alcohol. In these, the mixed solution which added methanol to the reaction solvent used at the time of reaction from a viewpoint which can carry out distillation collection | recovery easily is preferable. The amount of methanol at this time is usually preferably about 20 to 60% by mass in the total amount of the mixed solution, and water may be added to such an extent that the solubility of the fatty acid ester is not impaired. The amount of the mixed solvent used is the cellulose 100 used as a raw material in the production of alkali cellulose for the purpose of avoiding that the fatty acid ester is not uniformly dispersed, having no effect commensurate with the amount used, and becoming uneconomical. About 50 to 500 parts by mass is usually preferable with respect to parts by mass, and more preferably 100 to 400 parts by mass.

  The mixing of the hydroxyalkyl cellulose and the fatty acid ester is preferably performed under heating conditions from the viewpoint of avoiding that the fatty acid ester is not uniformly dispersed. The heating temperature is preferably about 20 to 80 ° C. from the viewpoint of the thermal stability of the hydroxyalkyl cellulose.

  The hydroxyalkyl cellulose composition of the present invention is excellent in dispersibility in water or the like, has a high dissolution rate, and has high transparency.

  Here, the dispersibility of the hydroxyalkyl cellulose composition in water can be determined by the state of occurrence of mamako when the hydroxyalkyl cellulose composition is poured into water at one time. Specifically, if the hydroxyalkyl cellulose composition charged into water becomes a transparent gel and does not generate mamako and the time required to disperse is within a predetermined time, hydroxy having excellent dispersibility in water. It can be judged as an alkylcellulose composition.

  The rate of dissolution of the hydroxyalkyl cellulose composition in water is determined by the time it takes to reach the final viscosity by measuring the viscosity (mPa · s) every hour by adding the hydroxyalkyl cellulose composition to water while stirring. it can. If this time is within a predetermined time, it can be judged that the solubility in water is excellent. The viscosity of the aqueous solution is measured using a BH type rotational viscometer at a temperature of 25 ° C.

  The transparency of the aqueous solution can be judged by the turbidity (ppm) measured using a turbidimeter (Mitsubishi Chemical Corporation, integrating sphere turbidimeter SEP-PT-706D). If it is 20 ppm or less, it can be judged as a highly transparent aqueous solution. When the turbidity of the aqueous solution exceeds 20 ppm, for example, there is a possibility that the appearance (designability) deteriorates when used in cosmetics and the like.

  Although the mechanism that exerts the action of excellent dispersibility in water and the like has not been elucidated, in general, hydroxyalkyl cellulose is powdery and has high hydrophilicity. Immediately after the body is put in, water is absorbed and the particle surface becomes a gel, and a lump (maco) is generated by the adhesive force. Once Mamako is formed, it is difficult for water to penetrate into the inside of the particles, making it difficult to obtain a uniform dispersion. However, in the composition of the present invention, by making the surface of the particles slightly hydrophobic with a specific fatty acid ester, it is presumed that excellent dispersibility can be realized without generation of mamaco when dispersed in water. .

  In addition, the mechanism of developing the effect of increasing the transparency of the aqueous solution is not yet elucidated, but the specific fatty acid ester has good affinity with hydroxyalkyl cellulose, and as a result, the transparency of the aqueous solution is low. Presumed to be higher.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Production example 1 of hydroxyalkyl cellulose
50 g of finely pulverized wood pulp as cellulose was immersed in 2000 g of a 20 wt% aqueous sodium hydroxide solution, and mixed and stirred in a 5 L flask at 30 ° C. for 30 minutes to allow alkali to act. Thereafter, the resulting mixture was subjected to pressure filtration to remove an aqueous sodium hydroxide solution and further pulverized to obtain 150 g of alkali cellulose.

  In a 1 L kneader, 150 g of the obtained alkali cellulose, 75 g of ethylene oxide and 50 g of methyl isobutyl ketone were charged at 15 ° C., and then mixed at the same temperature for 30 minutes, then heated to 50 ° C. and reacted for 3 hours.

  Next, a mixed solvent consisting of 450 g of methyl isobutyl ketone, 450 g of methanol and 100 g of water was added to the obtained reaction product to form a slurry. The resulting slurry was allowed to stand for several minutes, and then hydroxyethyl cellulose was filtered off.

  Further, a mixed solvent consisting of 225 g of methyl isobutyl ketone, 225 g of methanol and 50 g of water was added to the filtered hydroxyethyl cellulose to form a slurry, which was then filtered off in the same manner as described above. This operation was repeated twice to obtain 198 g of crude hydroxyethyl cellulose.

  The obtained crude hydroxyethyl cellulose was put in a 1 L kneader, charged with 50 g of a 10 wt% aqueous acetic acid solution, and stirred and mixed at 20 ° C. for 30 minutes.

  Next, the obtained mixture was dried overnight at 70 ° C. under reduced pressure to obtain 75 g of particulate hydroxyethyl cellulose (hydroxyethyl cellulose A).

Production example 2 of hydroxyalkyl cellulose
50 g of linter pulp finely pulverized as cellulose was immersed in 2000 g of a 20 wt% aqueous sodium hydroxide solution, and mixed and stirred in a 5 L flask at 30 ° C. for 30 minutes to allow alkali to act. Thereafter, the resulting mixture was subjected to pressure filtration to remove an aqueous sodium hydroxide solution and further crushed to obtain 160 g of alkali cellulose.

  In a 1 L kneader, 160 g of the obtained alkali cellulose, 80 g of ethylene oxide and 80 g of methyl isobutyl ketone were charged at 15 ° C., followed by mixing at the same temperature for 30 minutes, and then the temperature was raised to 50 ° C. and reacted for 3 hours.

  Next, a mixed solvent consisting of 500 g of methyl isobutyl ketone, 450 g of methanol and 50 g of water was added to the obtained reaction product to form a slurry. The resulting slurry was allowed to stand for several minutes, and then hydroxyethyl cellulose was filtered off.

  Further, a mixed solvent consisting of 250 g of methyl isobutyl ketone, 225 g of methanol and 25 g of water was added to the filtered hydroxyethyl cellulose to form a slurry, which was then filtered off in the same manner as described above. This operation was repeated three times to obtain 208 g of crude hydroxyethyl cellulose.

  The obtained crude hydroxyethyl cellulose was put in a 1 L kneader, charged with 50 g of a 10 wt% aqueous acetic acid solution, and stirred and mixed at 20 ° C. for 30 minutes.

  Next, the obtained mixture was dried overnight at 70 ° C. under reduced pressure to obtain 80 g of particulate hydroxyethyl cellulose (hydroxyethyl cellulose B).

Example 1
Hydroxyethyl cellulose A 75g was put into a 300mL kneader, and 0.375g of ethyl oleate (NOFABLE EO-85S, manufactured by NOF Corporation, 0.5 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose) was dissolved in 99g of methyl isobutyl ketone. The liquid was charged with stirring, heated to 50 ° C., mixed for 1 hour, and dried under reduced pressure at 70 ° C. overnight to obtain 75 g of a hydroxyethyl cellulose composition.

Example 2
The same procedure as in Example 1 was conducted except that 0.375 g of ethyl oleate in Example 1 was changed to 0.75 g of ethyl crotonate (manufactured by Wako Pure Chemicals, reagent grade 1) (1.0 part by mass with respect to 100 parts by mass of hydroxyethyl cellulose). As a result, 76 g of a hydroxyethyl cellulose composition was obtained.

Example 3
Except for changing 0.375 g of ethyl oleate in Example 1 to 3 g of ethyl caprate (manufactured by Wako Pure Chemicals, reagent grade 1) (4.0 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose), the same procedure as in Example 1 was performed. 78 g of a hydroxyethyl cellulose composition was obtained.

Example 4
The same procedure as in Example 1 was conducted except that 0.375 g of ethyl oleate in Example 1 was changed to 0.188 g of ethyl caproate (manufactured by Wako Pure Chemicals, reagent grade 1) (0.25 parts by mass relative to 100 parts by mass of hydroxyethyl cellulose). As a result, 75 g of a hydroxyethyl cellulose composition was obtained.

Example 5
Hydroxyethylcellulose B 75g was put in a 300mL kneader, 0.75g of ethyl oleate (NOFABLE EO-85S made by NOF Corporation) (1.0 parts by weight with respect to 100 parts by weight of hydroxyethylcellulose) 69.3g of methyl isobutyl ketone and 29.7% of methanol A solution dissolved in a mixed solvent of g was charged with stirring, heated to 50 ° C., mixed for 1 hour, and dried under reduced pressure at 70 ° C. overnight to obtain 76 g of a hydroxyethyl cellulose composition.

Example 6
Example 5 was the same as Example 5 except that 0.75 g of ethyl oleate was changed to 0.375 g of ethyl caprylate (manufactured by Wako Pure Chemicals, reagent grade 1) (0.5 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose). As a result, 75 g of a hydroxyethyl cellulose composition was obtained.

Example 7
In Example 5, 0.75 g of ethyl oleate was changed to 1.5 g of ethyl caprate (manufactured by Wako Pure Chemicals, grade 1 reagent) (2.0 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose). As a result, 77 g of a hydroxyethyl cellulose composition was obtained.

Comparative Example 1
In Example 1, 75 g of hydroxyethyl cellulose composition was obtained in the same manner as in Example 1 except that 0.375 g of ethyl oleate was not used.

Comparative Example 2
In Example 5, 75 g of a hydroxyethyl cellulose composition was obtained in the same manner as in Example 5 except that 0.75 g of ethyl oleate was not used.

Comparative Example 3
A solution obtained by adding 75 g of hydroxyethyl cellulose B in a 300 mL kneader and dissolving 2.5 g of 10 wt% glyoxal (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (0.33 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose) in 99 g of methyl isobutyl ketone The mixture was charged with stirring, heated to 50 ° C., mixed for 1 hour, and dried under reduced pressure at 70 ° C. overnight to obtain 75 g of a hydroxyethyl cellulose composition.

Comparative Example 4
Example 5 was the same as Example 5 except that 0.75 g of ethyl oleate was changed to 0.0375 g of ethyl caprylate (manufactured by Wako Pure Chemicals, reagent grade 1) (0.05 parts by mass with respect to 100 parts by mass of hydroxyethyl cellulose). As a result, 75 g of a hydroxyethyl cellulose composition was obtained.

Comparative Example 5
The same procedure as in Example 1 was conducted except that 0.375 g of ethyl oleate in Example 1 was changed to 4.5 g of ethyl caprate (manufactured by Wako Pure Chemicals, reagent grade 1) (6.0 parts by mass relative to 100 parts by mass of hydroxyethyl cellulose). As a result, 79 g of a hydroxyethyl cellulose composition was obtained.

Comparative Example 6
Example 5 was the same as Example 5 except that 0.75 g of ethyl oleate was changed to 0.75 g of lauric acid (manufactured by Wako Pure Chemicals, grade 1 reagent) (1.0 part by mass with respect to 100 parts by mass of hydroxyethyl cellulose). 76 g of a hydroxyethyl cellulose composition was obtained.

Comparative Example 7
Except for changing 0.375 g of ethyl oleate in Example 1 to 0.75 g of oleic acid (manufactured by Wako Pure Chemicals, reagent grade 1) (1.0 part by mass with respect to 100 parts by mass of hydroxyethyl cellulose), the same procedure as in Example 1 was performed. 75 g of a hydroxyethyl cellulose composition was obtained.

  About the hydroxyethylcellulose composition obtained by the Example and the comparative example, the dispersion time, the dissolution rate, and the turbidity of aqueous solution were measured and evaluated by the following methods. In addition, as a test sample for measurement, a pass product sieved with a 850 μm sieve was used. The results are shown in Table 1.

(1) Stirring dispersion time
(a) Dispersion time (time when Mamako disappears)
Into a 200mL beaker, add 147g of ion-exchanged water and use a magnetic stirrer (rotor: 13φ * 39mmL) to stir at a rotation speed of 500r / min. Then, the dispersion state of the hydroxyalkyl cellulose composition is visually observed to measure the time required for the hydroxyalkyl cellulose composition to completely disperse without producing mamako. If the time required for dispersion is 10 minutes or less, it can be determined that the dispersibility is excellent. In addition, when Mamako occurs without being dispersed even after 60 minutes, the dispersion time is evaluated as “60 <”.
(b) Viscosity development time Measure the time for the liquid level to become horizontal without swirling by stirring.

(2) Dissolution rate
Put 245g of ion-exchanged water into a 500mL beaker and gradually stir the 5g hydroxyethylcellulose so that it does not become mamako while stirring at a rotation speed of 700r / min using a stirrer equipped with a 4-blade paddle (blade diameter: 50mm). The viscosity (mPa · s) is measured every 5 minutes, 10 minutes, 20 minutes, 30 minutes, 60 minutes, and 120 minutes, and the time required to reach the final reached viscosity is measured. If the said time is 20 minutes or less, it can be judged that the solubility is excellent. The aqueous solution viscosity of the obtained hydroxyethyl cellulose composition is measured using a B-type rotational viscometer (product number: VS-H1 type, manufactured by Shibaura System Co., Ltd.) at 25 ° C. and 20 r / min.

(3) Turbidity (2) The sample that reached the final viscosity obtained in the dissolution rate test was measured using a turbidimeter (manufactured by Mitsubishi Chemical Corporation, integrating sphere turbidimeter SEP-PT-706D). .

From Table 1, it can be seen that the hydroxyethyl cellulose compositions obtained in Examples 1 to 7 are excellent in dispersibility in water, exhibit viscosity in a short time, and obtain a highly transparent aqueous solution.
In contrast, the hydroxyethyl cellulose compositions of Comparative Examples 1 and 2 in which no fatty acid ester is blended and Comparative Example 4 in which the blending amount of the fatty acid ester is too small lacks dispersibility in water and has a slow dissolution rate. The conventionally used hydroxyethyl cellulose composition of Comparative Example 3 to which glyoxal is added is excellent in water dispersibility, but has a low dissolution rate.
Moreover, the comparative example 5 with too much compounding amount of fatty acid ester has a problem in quality because the transparency of the aqueous solution deteriorates. In Comparative Examples 6 and 7 using a fatty acid instead of the fatty acid ester, the viscosity of the aqueous solution is increased and the transparency is deteriorated.

  The hydroxyalkyl cellulose composition of the present invention can be used as a thickener for paints and cosmetics, a stabilizer for emulsion polymerization, a binder for pharmaceutical tablets, a film coating material, and the like.

Claims (3)

Hydroxyalkyl cellulose composition containing 0.1 to 5 parts by mass of fatty acid ester with respect to 100 parts by mass of hydroxyalkyl cellulose , wherein the fatty acid ester has 4 to 30 carbon atoms, saturated or unsaturated fatty acid and carbon number 1 A hydroxyalkyl cellulose composition, which is an ester of ˜22 with a monohydric alcohol . Fatty acid ester is ethyl caproate, ethyl caprylate, ethyl caprate, isopropyl myristate, ethyl stearate, isopropyl stearate, octyl stearate, ethylhexyl stearate, octadecyl stearate, ethyl isostearate, tridecyl isostearate, crotonic acid Group consisting of ethyl, methyl oleate, ethyl oleate, octyl oleate, dodecyl oleate, octyldodecyl oleate, oleyl oleate, ethyl linoleate, isopropyl linoleate, oleyl linoleate, ethyl linolenate and ethyl coconut fatty acid ethyl The hydroxyalkyl cellulose composition according to claim 1 , wherein the hydroxyalkyl cellulose composition is at least one selected from the group. The hydroxyalkyl cellulose composition according to claim 2 , wherein the fatty acid ester is at least one selected from the group consisting of ethyl caproate, ethyl caprylate, ethyl caprate, ethyl crotonic acid and ethyl oleate.