JP5352219B2 - Method for producing cationized galactomannan polysaccharide - Google Patents

Description

  The present invention relates to a method for producing a cationized galactomannan polysaccharide.

As a method for cationizing a polysaccharide, an organic solvent method, a water medium method, a dry method, and the like are known.
Patent Document 1 discloses a cationized guar gum characterized by reacting a cationizing agent or a mixture thereof after dissolving or dispersing guar gum in an aqueous medium having a water-soluble organic solvent content of 40% by weight or less. A manufacturing method is described. However, in this method, since a large amount of water is used, the reaction efficiency of the cationizing agent is reduced, and the polysaccharide dissolves in water and becomes high viscosity, so that stirring is not easy, and high quality and homogeneous. There is a drawback that it is not easy to obtain a cationized polysaccharide.

  In Patent Document 2, a polysaccharide such as galactomannans is reacted with a quaternary ammonium compound having a glycidyl group after adding an alkaline agent in a mixed solvent of a certain amount or less of water and a lower alcohol. A method of cationization is described. However, this method has a problem that the reaction efficiency and the whiteness are lowered because the alkali agent to be added and the quaternary ammonium compound having a glycidyl group are added all at once and a lower alcohol is used.

JP 9-176203 A Japanese Patent Laid-Open No. 6-18001

  An object of the present invention is to provide a method for easily and easily producing a high-quality cationized galactomannan polysaccharide.

The inventors of the present invention can easily and easily produce a high-quality cationized product by cationizing a galactomannan-based polysaccharide at a rate of addition of a specific alkaline agent under a reduced amount of water or solvent. I found.
That is, this invention provides the manufacturing method of the cationized galactomannan-type polysaccharide which has the following process (1) and (2).
Step (1): Average addition rate of water and alkali metal hydroxide to galactomannan polysaccharide (number of moles of alkali metal hydroxide / number of moles of hydroxyl group of galactomannan polysaccharide) Step (2) to obtain a mixture containing galactomannan polysaccharide by adding 0001 to 0.1: Add a quaternary ammonium compound having a glycidyl group to the mixture obtained in step (1), The galactomannan polysaccharide is cationized under the condition that the water content in the reaction system is 4 to 35 parts by weight with respect to 100 parts by weight (dry weight) of the galactomannan polysaccharide. Step of obtaining a polysaccharide

  According to the present invention, a high-quality cationized galactomannan polysaccharide having high transparency and whiteness can be easily produced.

The method for producing a cationized galactomannan polysaccharide of the present invention is characterized by having the following steps (1) and (2).
Step (1): Average addition rate of water and alkali metal hydroxide to galactomannan polysaccharide (number of moles of alkali metal hydroxide / number of moles of hydroxyl group of galactomannan polysaccharide) Step of adding 0001 to 0.1 to obtain a mixture containing a galactomannan polysaccharide Step (2): A quaternary ammonium compound having a glycidyl group is added to the mixture obtained in step (1), The galactomannan polysaccharide is cationized under the condition that the water content in the reaction system is 4 to 35 parts by weight with respect to 100 parts by weight (dry weight) of the galactomannan polysaccharide. Steps for obtaining polysaccharides Hereinafter, each component and step used in the present invention will be described.

(Galactomannan polysaccharide)
Galactomannan polysaccharides (hereinafter also referred to as “raw polysaccharides”) are neutral polysaccharides in which the main chain of mannose is a galactose unit as a side chain. It is abundant in seeds of family plants.
The raw material polysaccharide used in the present invention is not particularly limited, but in particular, guar gum obtained from the endosperm part of guar beans (mannose: galactose ratio = about 2: 1), tara gum obtained from the endosperm part of legume cod seeds ( Mannose: galactose ratio = about 3: 1), locust bean gum obtained from the endosperm portion of legume carob tree seeds (mannose: galactose ratio = about 4: 1), fenugreek gum obtained from fenugreek seeds (mannose: galactose One or more selected from a ratio = about 1: 1) are preferred. These galactomannan-based polysaccharides are preferably used as fine powders, and are preferably purified to remove impurities as much as possible.

(Alkali metal hydroxide)
The alkali metal hydroxide used in the present invention serves as a catalyst when the raw material polysaccharide reacts with a quaternary ammonium compound having a glycidyl group. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable.

(Quaternary ammonium compound having a glycidyl group)
In the present invention, a quaternary ammonium compound having a glycidyl group (hereinafter also simply referred to as “quaternary ammonium compound”) is used as a cationizing agent. The quaternary ammonium compound is preferably a compound represented by the following general formula (1). This compound is known as a cationizing agent for starch.

Here, Y represents a linear or branched alkanediyl group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, and R ¹ , R ² and R ³ are 1 to 5 carbon atoms, preferably Represents a linear or branched alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and X represents a halogen atom. A preferred example of the aryl group is a benzyl group, and a preferred example of the halogen atom is a chlorine atom.
The quaternary ammonium compound represented by the general formula (1) is usually solid at room temperature and has a property of being well dissolved in water. A preferred example of this compound is glycidyltrimethylammonium chloride.

[Step (1)]
Step (1) is an average addition rate of water and alkali metal hydroxide to galactomannan polysaccharide (number of moles of alkali metal hydroxide / number of moles of hydroxyl group possessed by galactomannan polysaccharide) 0 It is a step of adding 0001 to 0.1 to obtain a mixture containing a galactomannan polysaccharide.
In the step (1), it is preferable to add an alkali metal hydroxide aqueous solution previously dissolved in water to the raw material polysaccharide, and then stir this well. Thereby, the hydroxyl group of the raw material polysaccharide is alkali-treated to form an alcoholate.

In the present invention, the alkali metal hydroxide is added under the condition that water is reduced and essentially no organic solvent is used. From the viewpoint of reaction efficiency, transparency, and whiteness, the average addition of the alkali metal hydroxide is added. The speed is as follows:
The average addition rate of alkali metal hydroxide to galactomannan polysaccharide (number of moles of alkali metal hydroxide / number of moles of hydroxyl group of galactomannan polysaccharide) is 0.0001 to 0.1. , Preferably 0.0002 to 0.05, more preferably 0.0005 to 0.01, still more preferably 0.0008 to 0.008.
The addition rate is not necessarily constant, and may be continuous or intermittent, but the average addition time is within the above range.
The method for adding the alkali metal hydroxide is not particularly limited, but continuous dripping is preferred.
The addition amount of the alkali metal hydroxide is determined from the viewpoint of reaction efficiency as a catalyst and whiteness and transparency of the obtained galactomannan polysaccharide (number of moles of alkali metal hydroxide / galactomannan polysaccharide The ratio of the number of moles of hydroxyl groups possessed is preferably 0.001 to 0.3, more preferably 0.01 to 0.1.

The addition amount of the alkali metal hydroxide in the reaction system is preferably 1 to 8 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight (dry weight) of the raw material polysaccharide. Within this range, the cationization reaction proceeds uniformly, the cationization reaction product does not partially gelatinize, and a good product can be obtained, and after completion of the reaction, an alkali metal hydroxide is added. When neutralized with acid, a large amount of salt is formed and does not adversely affect product quality.
The temperature at the time of addition is preferably kept at 0 to 40 ° C., more preferably 10 to 35 ° C., from the viewpoint of smoothly promoting the production of the alcoholate.
The temperature at the time of addition can be controlled by, for example, the temperature of the cooling medium flowing through the jacket of the mixing apparatus and its flow rate.

[Step (2)]
In step (2), a quaternary ammonium compound having a glycidyl group is added to the mixture obtained in step (1), and the water content in the reaction system is 100 parts by weight (dry weight) of galactomannan polysaccharide. ) To cationize the galactomannan polysaccharide under a condition of 4 to 35 parts by weight to obtain a cationized galactomannan polysaccharide.

Water is necessary for reacting the raw material polysaccharide with the alkali metal hydroxide to uniformly produce the alcoholate of the raw material polysaccharide.
The quaternary ammonium compound having a glycidyl group is preferably dissolved in water and used in the form of an aqueous solution. It is preferable to continue stirring after the quaternary ammonium compound aqueous solution is added to advance the cationization reaction.
In this case, the amount of water is 4 to 35 parts by weight, preferably 10 to 10 parts by weight with respect to 100 parts by weight of the dry weight of the raw material polysaccharide, including the water to be added and the water contained in the raw material polysaccharide. 30 parts by weight. Within this range, the formation of the alcoholate is facilitated, the gelatinization of the reaction product is suppressed, and the reduction in reaction efficiency and coloring are suppressed. In addition, the quaternary ammonium compound is hydrolyzed to suppress a decrease in reactivity.
Since water is usually contained in the dried raw material polysaccharide by about several percent, it may not be necessary to add water when the wet raw material polysaccharide is used.

The quaternary ammonium compound having a glycidyl group is cationized by reacting with an alcoholate in which the hydroxyl group of the raw material polysaccharide is alkali-treated. The alkali metal is reused as a catalyst. Therefore, it is preferable to adjust the addition rate of the quaternary ammonium compound having a glycidyl group as follows.
The average addition rate of the quaternary ammonium compound having a glycidyl group with respect to the galactomannan polysaccharide (number of moles of the quaternary ammonium compound having glycidyl group / number of moles of the hydroxyl group of the galactomannan polysaccharide) is reaction efficiency, From the viewpoint of whiteness and transparency, it is preferably 0.0001 to 0.3, more preferably 0.0005 to 0.05, and still more preferably 0.0005 to 0.01.
The addition rate is not necessarily constant, and may be continuous or intermittent, but the average addition time is within the above range.

The addition amount of the quaternary ammonium compound having a glycidyl group is such that the quaternary ammonium with respect to the number of moles of the hydroxyl group of the galactomannan polysaccharide from the viewpoint of reaction efficiency and conditioning properties as a shampoo of the obtained galactomannan polysaccharide. The ratio of the number of moles of the compound (number of moles of quaternary ammonium compound having a glycidyl group / number of moles of hydroxyl group of the galactomannan polysaccharide) is preferably 0.0001 to 0.3, more preferably 0.001 to 0.2, more preferably 0.01 to 0.1.
The addition amount of the quaternary ammonium compound having a glycidyl group is preferably 5 to 60 parts by weight and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the dry weight of the raw material polysaccharide from the same viewpoint as described above. Part.
The ratio of (number of moles of glycidyltrimethylammonium chloride / number of moles of alkali metal hydroxide) is preferably 0.1 to 10, more preferably 0.5 to 5, from the viewpoint of reaction efficiency.
From the viewpoint of reaction efficiency, it is preferable to carry out the reaction under conditions in which a water-soluble organic solvent, particularly an alcohol-based water-soluble organic solvent is substantially absent. “Substantially absent” means that the content of the water-soluble organic solvent in the reaction system is preferably 3 parts by weight or less, more preferably 1 part by weight or less with respect to 100 parts by weight (dry weight) of the raw material polysaccharide. It means that. Examples of the alcohol-based water-soluble organic solvent include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, and butanol. Examples of other water-soluble organic solvents include acetone.

The temperature at the time of addition is preferably kept at 40 to 80 ° C, more preferably 50 to 75 ° C, from the viewpoint of allowing the reaction to proceed smoothly. Then, the quaternary ammonium compound reacts with the alcoholate of the raw material polysaccharide to produce a cationized product. Since the obtained cationized product is alkaline, it can be neutralized by adding an acid, for example, acetic acid, and dried under reduced pressure to remove water to obtain the desired high-quality cationized galactomannan polysaccharide. it can.
The temperature during the mixing reaction can be controlled by, for example, the temperature of the cooling medium flowing through the jacket of the mixing device and the flow rate thereof.

(Mixed reactor)
There is no restriction | limiting in particular in the mixing reactor used by this invention. For example, a mixing device such as a kneader, a planetary mixer, or a Banbury mixer can be used. Specific examples of commercially available products include Kneader (Irie Shokai Co., Ltd.), Redige Mixer (manufactured by Redige Corporation), Proshare Mixer (manufactured by Taiheiyo Kiko Co., Ltd.), Axial Mixer (manufactured by Sugiyama Heavy Industries, Ltd.), Nauta Mixer ( Hosokawa Micron Co., Ltd.), High Speed Mixer (Fukae Bautech Co., Ltd.), Henschel Mixer (Mitsui Mine Co., Ltd.) and the like.
Among these, a kneader is preferable from the viewpoint of strong shear stress and easy control of operating conditions.
As described in the Chemical Engineering Association edition “Chemical Engineering Handbook”, revised edition 5 (published by Maruzen Co., Ltd.), pages 917 to 919, there are two types of kneaders: batch type and continuous type. Examples of the latter include a self-cleaning type kneader. Among these, a double-arm kneader is preferable from the viewpoints of product type switching, tank cleaning, and the like.

A double-arm kneader typically has a rotating blade fixed to two rotating shafts attached in parallel to the twin body of the lower half of the stirring tank, and the gap between the rotating blade and the stirring tank, and between the rotating blade and the rotating blade. And kneading operation is performed. The rotor blades rotate in opposite directions at the same speed or different speeds, and give shearing / compression action and the like. The double-arm kneader includes a normal pressure type (open type) and a pressure type (sealed type), either of which can be used.
There are no particular restrictions on the type of kneader blade. Specifically, a rotary blade such as a Banbury type, a sigma type, a zet type, a spiral type (135 ° spiral type, 180 ° spiral type), a fishtail type, a sawtooth type, or the like can be used. Among these, Banbury type and sigma type rotor blades are preferable.

(Cationized galactomannan polysaccharide)
The cationized galactomannan polysaccharide obtained as described above can be neutralized, washed, and dried under reduced pressure by a conventional method, if necessary.
The obtained cationized product is useful as a raw material for cosmetics, detergents, fiber treatment agents and the like, and in particular, cationized products of guar gum, tara gum, locust bean gum, etc. are used in shampoos and hair cosmetics and can be easily washed. Creamy foam quality, slipperiness, and softness can be imparted.

In the following examples and comparative examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified. In addition, the moisture content, reaction efficiency, substitution degree of cationized product, whiteness, and transmittance of the raw material polysaccharide were measured by the following methods.
(1) Moisture content of raw material polysaccharide It measured using the infrared moisture meter.
(2) The reaction efficiency was calculated from the following formula (when guar gum was used).
Reaction efficiency (%) = [(degree of substitution of the obtained cationized guar gum) × (charge amount of guar gum (g) / 162) / (charge amount of glycidyltrimethylammonium chloride (g) / 152)] × 100
In the above formula, “152” is the molecular weight of glycidyltrimethylammonium chloride, and “162” is the molecular weight of the anhydrous monosaccharide unit.

(3) Degree of substitution It calculated from the following formula from the nitrogen content (N) wt% of the cationized polysaccharide measured with a CHN elemental analyzer (trade name: VARIO ELIII, manufactured by Elemental Co.).
Degree of substitution = 162N / (1400-152N)
This degree of substitution indicates the degree of cationization and is a value indicating the number of moles of cationic groups added per anhydrous monosaccharide unit of the raw material polysaccharide.
(4) Whiteness (WH)
Using a color difference meter (CR-200, manufactured by Konica Minolta Holdings, Inc.), WH = 100 − ((100−L) ² , measured from the bottom of a 50 ml screw tube containing a cationized polysaccharide powder sample. + A ² + b ² ) ^Obtained from ^0.5 .
(5) Transmittance A 1% aqueous solution of a cationized polysaccharide was prepared and measured at a wavelength of 600 nm using a spectrophotometer (manufactured by Hitachi, Ltd., U-2000A).

Example 1
A 1 L kneader (Irie Shokai Co., Ltd., trade name: PNV-1 type, rotary blade: sigma type) was charged with 190 parts (product name: GRINDSTED GUAR 175) (water content 10%), 14 parts of 30% by weight aqueous sodium hydroxide solution was added dropwise over 30 minutes.
Further, after stirring and mixing for 30 minutes, vacuum deaeration was performed until the pressure in the container reached 26.7 kPa, and nitrogen substitution was performed twice to leak to normal pressure with nitrogen. The mixture was heated to 70 ° C. with stirring, and 42 parts of an 80 wt% glycidyltrimethylammonium chloride aqueous solution (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name: SY-GTA80, purity 90 wt%) was added dropwise over 1 hour.
Furthermore, after heating and mixing at 70 ° C. for 4 hours, the mixture was cooled to room temperature, and the cationized galactomannan polysaccharide obtained above was neutralized with acetic acid. The neutralized product was sufficiently washed with an 85 wt% 2-propanol aqueous solution to remove unreacted glycidyltrimethylammonium chloride and the like, and then dried to obtain a cationized guar gum.
The degree of substitution of the obtained cationized guar gum was 0.17, and the reaction efficiency was as high as 89%. The whiteness was 68 and the transmittance was 36%.

The average dropping rate of the aqueous sodium hydroxide solution in steps (1) and (2) was as follows.
[Step (1)]
The number of moles of hydroxyl groups that the galactomannan polysaccharide has is
190 × 0.9 × 3 (average number of hydroxyl groups per anhydrous monosaccharide) /162=3.17.
The number of moles of alkali metal hydroxide is 14 × 0.3 / 40 = 0.105.
Therefore, the average dropping rate of the aqueous sodium hydroxide solution in this case (number of moles of alkali metal hydroxide / number of moles of hydroxyl group of the galactomannan polysaccharide) is as follows:
It was 0.105 / 3.17 / 30 = 0.0011.
[Step (2)]
The number of moles of glycidyltrimethylammonium chloride is
42 × 0.8 × 0.9 / 152 = 0.199.
Therefore, in this case, the average dropping rate of the aqueous glycidyltrimethylammonium chloride solution (number of moles of quaternary ammonium compound having a glycidyl group / number of moles of hydroxyl group of a galactomannan polysaccharide) is as follows:
It was 0.199 / 3.17 / 60 = 0.00104.

Example 2
A cationized tara gum was obtained in the same manner as in Example 1 except that tara gum (manufactured by Sanki Co., Ltd., trade name: spino gum) was used instead of guar gum used in Example 1 and reacted at 60 ° C. for 10 hours.
The degree of substitution of the obtained cationized tara gum was 0.16, and the reaction efficiency was a high value of 84%. The whiteness was 78, and the transmittance was 48%.

Example 3
Instead of guar gum used in Example 1, locust bean gum (manufactured by Sanki Co., Ltd., trade name: MEYPRO LBG FLEUR M-200) was used, and an 80 wt% glycidyltrimethylammonium chloride aqueous solution (Sakamoto Pharmaceutical Co., Ltd., Cationized locust bean gum was obtained in the same manner except that it was reacted with 76 parts (trade name: SY-GTA80, purity 90% by weight) at 60 ° C. for 10 hours.
The degree of substitution of the obtained cationized locust bean gum was 0.27, and the reaction efficiency was as high as 82%. The whiteness was 79, and the transmittance was 49%.

Comparative Example 1
After adding 150 parts of guar gum (trade name: GRINDSTED GUAR 175, product name: GRINDSTED GUAR 175) to a 1 L kneader (Irie Shokai, PNV-1 type), 6 parts of water and 24 parts of methanol And 6 parts of sodium hydroxide were added separately (addition time: about 2 seconds), and then stirred at room temperature for 2 hours. A mixed solution of 60 parts of 80% by weight glycidyltrimethylammonium chloride aqueous solution (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, purity 90% by weight) and 30 parts of methanol is added all at once (addition time: about 5 seconds). It was. The vessel was degassed under reduced pressure until the pressure in the vessel reached 26.7 kPa, and nitrogen replacement was performed twice with nitrogen to leak to normal pressure, followed by heating to 70 ° C. and stirring for 4 hours. Then, it neutralized with acetic acid. The solution was thoroughly washed with 85% by weight 2-propanol aqueous solution and dried to obtain a cationized guar gum.
The degree of substitution of the obtained cationized guar gum was 0.14, and the reaction efficiency was a low value of 42%. The whiteness was 60 and the transmittance was 29%.

The average dropping rate of the aqueous sodium hydroxide solution in steps (1) and (2) was as follows.
[Step (1)]
The number of moles of hydroxyl groups that the galactomannan polysaccharide has is
150 × 0.9 × 3 (average number of hydroxyl groups per anhydrous monosaccharide) /162=2.5
The number of moles of alkali metal hydroxide is 6/40 = 0.15.
Therefore, the average dropping rate of the aqueous sodium hydroxide solution in this case (number of moles of alkali metal hydroxide / number of moles of hydroxyl group of the galactomannan polysaccharide) is as follows:
It was 0.15 / 2.5 / 0.033 = 1.818.
[Step (2)]
The number of moles of glycidyltrimethylammonium chloride is
60 × 0.8 × 0.9 / 152 = 0.284
Therefore, in this case, the average dropping rate of the aqueous glycidyltrimethylammonium chloride solution (number of moles of quaternary ammonium compound having a glycidyl group / number of moles of hydroxyl group of a galactomannan polysaccharide) is as follows:
It was 0.284 / 2.5 / 0.083 = 1.368.

  According to the present invention, since the raw material polysaccharide is reacted in a reaction system having a low water content, stirring is easy, a large reaction vessel is not required, and the cationization reaction can be efficiently advanced. Moreover, the obtained cationized galactomannan-based polysaccharide is of high quality and is useful as a raw material for cosmetics, cleaning agents, fiber treatment agents and the like.

Claims (4)

The manufacturing method of the cationized galactomannan-type polysaccharide which has the following process (1) and (2).
Step (1): to galactomannan polysaccharides, (moles / min of hydroxyl groups of moles / galactomannan polysaccharides of alkali metal hydroxide) to A alkali metal hydroxide solution average addition rate 0.0001 Step of obtaining a mixture containing galactomannan polysaccharide by adding at ˜0.1 Step (2): A quaternary ammonium compound having a glycidyl group is added to the mixture obtained in Step (1) and reacted. The water content in the system is 4 to 35 parts by weight with respect to 100 parts by weight (dry weight) of the galactomannan polysaccharide , and the alcohol-based water-soluble organic solvent in the reaction system is A step of obtaining a cationized galactomannan polysaccharide by cationizing the galactomannan polysaccharide under a condition of 3 parts by weight or less with respect to 100 parts by weight (dry weight) of the saccharide.   The cationization according to claim 1, wherein in step (1), the addition amount of the alkali metal hydroxide in the reaction system is 1 to 8 parts by weight with respect to 100 parts by weight (dry weight) of the galactomannan polysaccharide. A method for producing a galactomannan polysaccharide. In step (2), the average addition rate of quaternary ammonium compound having a glycidyl group (number of moles of quaternary ammonium compound having glycidyl group / number of moles of hydroxyl group of galactomannan polysaccharide) 0.0001 to The method for producing a cationized galactomannan polysaccharide according to claim 1 or 2 , which is added at 0.3. The method for producing a cationized galactomannan polysaccharide according to any one of claims 1 to 3 , wherein the galactomannan polysaccharide is at least one selected from guar gum, tara gum, locust bean gum, and fenugreek gum.