JPH1112011A - Additive for mortar - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive excellent in finishing properties by a plasterer, by including a polysaccharide derivative prepared by substituting the hydrogen atoms of the hydroxyl groups of a polysaccharide or its alkylated derivative with a hydrophobic substituent group containing a hydrocarbon chain as a partial structure and a hydrophilic substituent group containing a group selected from a sulfonic group, etc., as a partial structure. SOLUTION: This additive for a mortar contains a polysaccharide derivative obtained by substituting hydrogen atoms of a part or the whole hydroxyl groups of a polysaccharide or its alkylated or hydroxy alkylated derivative with (A) a hydrophobic substituent group containing a 8-40C hydrocarbon chain as a partial structure and (B) an ionic hydrophilic substituent group containing one or more groups selected from the group consisting of a sulfonic group, a carboxyl group, a sulfate group and their salts as a partial structure. The admixture is mixed with a cement material and a fine aggregate to give a mortar composition. The degree of substitution of the substituent A is 0.0001-1 based on the constituent monosaccharide residue and that of the substituent B is 0.001-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mortar additive and a mortar composition containing the additive. More specifically, the present invention relates to an additive for mortar used for various purposes such as foundation and finishing, whether it is wooden construction, concrete construction, or the like, and which has excellent finishability and coagulation. The present invention relates to an additive capable of providing a mortar composition having a very small delay in strength and a delay in strength development.

[0002]

2. Description of the Related Art Cement mortar, which is generally called mortar, is made by mixing sand as a fine aggregate with a cement as a main raw material, and in some cases, lightweight plastic foam.
It is indispensable in the field of construction and construction as a base for painting, brickwork, masonry, tile attachment, etc., and as a material for surface finishing.

[0003] In order to use mortar as a base material or a finishing material, it is necessary to perform plastering work (plastering finish) by adding water to a cementitious material and sand, kneading the mixture, and applying the mixture with a trowel. However, plastering is an operation that requires some skill. Therefore, conventionally, a water-soluble polymer such as methylcellulose or hydroxymethylcellulose has been mixed into mortar for the purpose of imparting water retention and plasticity for facilitating Sana finishing. By blending these water-soluble polymers, it is relatively easy to finish Saka with skill.

[0004]

However, the above-mentioned water-soluble polymer has the property of inhibiting the hydration reaction of cement. For this reason, the workability itself is improved, but there is a problem that the setting of the mortar that has been carried out is delayed, the strength is reduced, and the construction period is delayed. Therefore, an object of the present invention is to provide an additive capable of providing an excellent mortar composition, which has no problems of setting retardation and strength reduction while improving plaster finish, and a mortar composition thus obtained. Is to do.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the hydroxyl group of the polysaccharide or its derivative is converted to a hydrophobic group such as a long-chain alkyl glyceryl ether group and a sulfonic acid group. The polysaccharide derivative obtained by substitution with an ionic hydrophilic group such as the above shows a large thickening effect even in an extremely small amount under strong ionic strength, and when this is used as an additive for mortar, the water-soluble As in the case where the molecule is added, it has been found that good plaster finish is obtained, the delay in setting is small, and the initial strength is extremely excellent. The present invention has been completed based on this finding.

That is, the present invention relates to a hydrophobic substituent wherein a part or all of the hydrogen atoms of a hydroxyl group of a polysaccharide or an alkylated or hydroxyalkylated derivative thereof has a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure. A) and an ionic hydrophilic substituent (B) containing, as a partial structure, at least one group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphate group, and a sulfate group, and salts thereof. It is an additive for mortar containing a substituted polysaccharide derivative. Further, the present invention also provides a mortar composition containing such an additive together with a cementitious material and further with a fine aggregate.

[0007]

According to the present invention, a polysaccharide derivative used as a thickener is a polysaccharide or an alkylated or hydroxyalkylated derivative thereof, wherein some or all of the hydrogen atoms of the hydroxyl groups are hydrophobically substituted. It is substituted with a group (A) and an ionic hydrophilic substituent (B). Hydrophobic substituent (A)
Has, as a partial structure, a hydrocarbon chain having 8 to 40 carbon atoms, which is more specifically, a hydrocarbon chain having 8 to 40 carbon atoms, preferably
An alkyl glyceryl ether group having a linear or branched alkyl group of 12 to 36, more preferably 16 to 24, or an alkenyl glyceryl ether group having a linear or branched alkenyl group having a similar carbon number, or a hydroxyl group is substituted. May be a straight-chain or branched alkyl group having 8 to 40 carbon atoms, preferably 12 to 36, more preferably 16 to 24, which may have an oxycarbonyl group inserted therein, an alkenyl group or an acyl group. is there. From the viewpoint of ease of production and other viewpoints, an alkyl glyceryl ether group, a long-chain alkyl group, and a 2-hydroxy long-chain alkyl group are preferred, and an alkyl glyceryl ether group is particularly preferred. Here, the alkyl glyceryl ether group refers to the structure of the remaining portion of the alkyl glyceryl ether except for one hydroxyl group. More specifically, as the alkyl glyceryl ether group, a 2-hydroxy-3-alkoxypropyl group, 2-
Examples thereof include an alkoxy-1- (hydroxymethyl) ethyl group, a 2-hydroxy-3-alkenyloxypropyl group, and a 2-alkenyloxy-1- (hydroxymethyl) ethyl group. These hydrophobic substituents (A) may be substituted with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to a polysaccharide molecule.

The ionic hydrophilic substituent (B) is a substituent containing, as a partial structure, at least one group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphate group and a sulfate group. May form a salt. Specifically, a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a salt thereof, a carboxyalkyl group or a salt thereof, an alkyl phosphate group or a salt thereof, a sulfate ester alkyl group or a salt thereof, and the like Is mentioned. Preferably, it is a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group. More specifically, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfoethyl group
2-hydroxypropyl group, 2-sulfo-1- (hydroxymethyl) ethyl group and the like, all or a part of which are alkali metals such as Na and K, alkaline earth metals such as Ca and Mg, amines Or a salt with an organic cation group such as a salt, an ammonium ion, or the like.

[0009] These polysaccharide derivatives according to the present invention change in solubility in kneading water and thickening depending on the degree of substitution by the hydrophobic substituent (A) and the ionic hydrophilic substituent (B). That is, by setting the degree of substitution between the hydrophobic substituent (A) and the ionic hydrophilic substituent (B) within a preferable range, it is possible to obtain appropriate solubility and viscosity in kneading water. Excellent plaster finish can be imparted to the mortar. From such a viewpoint, the degree of substitution by the hydrophobic substituent (A) is 0.000 per unit of the constituent monosaccharide residue.
01 to 1, and more preferably 0.0005 to 0.01. The degree of substitution by the ionic polar substituent (B) is as follows:
It is 0.001-2 per unit, and 0.01-1 is more preferable. A particularly preferred degree of substitution is 0.000 for the hydrophobic substituent (A).
07 to 0.005, and the ionic hydrophilic substituent (B) is 0.02
~ 0.15.

In the present invention, polysaccharides include cellulose; starch; rhizome polysaccharides such as konjac mannan and trolloa sticky substances; gum arabic, tragacanth gum;
Sap polysaccharides such as karaya gum; seed polysaccharides such as locust bean gum, guar gum, tamarind gum; seaweed polysaccharides such as agar, carrageenan, algin; animal polysaccharides such as chitin, chitosan heparin, chondroitin sulfate; dextran, xanthan gum, etc. Microbial polysaccharides. Examples of the ionic groups substituted include anionic group-substituted products such as carboxymethyl cellulose, cellulose sulfate, cellulose phosphate and cellulose phosphite. Examples of the alkylated or hydroxyalkylated derivative of the polysaccharide include hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl Starch, hydroxyethylmethylcellulose, hydroxyethylmethylguar gum, hydroxyethylmethylstarch, hydroxypropylmethylcellulose, hydroxypropylmethylguar gum, hydroxypropylmethylstarch and the like, among which cellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, hydroxypropylcellulose Cellulose and its derivatives are preferable. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group and hydroxypropyl group of these polysaccharides may be substituted with a single substituent,
It may be substituted with a plurality of substituents, and the degree of substitution per constituent monosaccharide residue is preferably from 0.1 to 5, particularly preferably from 0.5 to 3. When the substituent is an alkyleneoxy group, the degree of substitution, that is, the number of moles added per constituent monosaccharide residue is 0.1.
To 10, particularly preferably 0.5 to 5. Further, the weight average molecular weight of these polysaccharides or derivatives thereof is 10,000 to 10,000,000, and particularly preferably 100,000 to 5,000,000.

The substituted polysaccharide derivative of the present invention partially hydrophobizes (introduces a hydrophobic substituent (A)) or hydrophilizes a hydrogen atom of a hydroxyl group of a polysaccharide or an alkylated or hydroxyalkylated derivative thereof. After the introduction of the ionic hydrophilic substituent (B)), part or all of the remaining hydroxyl groups can be hydrophilized or hydrophobized, respectively, or by performing hydrophobization and hydrophilization simultaneously.

The introduction of a substituent can be carried out, for example, as follows. That is, a polysaccharide or a derivative thereof is converted into an alkyl or alkenyl glycidyl ether having 8 to 40 carbon atoms in the presence of an alkali,
A hydrophobic substituent by reacting with an epoxide, halide, halohydrin, acyl halide, or an ester or carboxylic anhydride having an acyl group having 8 to 40 carbon atoms of a linear or branched saturated or unsaturated alkyl having from 40 to 40 (A) is introduced, and vinyl sulfonic acid or a haloalkanesulfonic acid having 1 to 5 carbon atoms which may be substituted with a hydroxyl group in the presence of an alkali, a halocarboxylic acid, a halophosphate ester, a halosulfate ester or a salt thereof And the like.

The cementitious material to which the mortar additive of the present invention containing the above-mentioned polysaccharide derivative is added is an inorganic substance which shows curability when kneaded with water, and is typically Portland cement. Blast furnace cement, silica cement and the like, but are not limited thereto.

The amount of the mortar additive to be added to the cementitious material according to the present invention can be appropriately determined according to the desired degree of thickening and finishability. 0.0001- polysaccharide derivative
It is preferable that the composition is 0.03% by weight.
% By weight is preferable in terms of balance between workability and cost.

The addition of the additive to the cementitious material is as follows:
It can be in the form of an aqueous solution or powder, and the addition time may be before kneading the mortar, such as dry blending with a cementitious material and fine aggregate, dissolution in kneading water, or the like. It is also possible to add it during the kneading period, that is, at the same time as or immediately after the water is injected into the cementitious material and before the kneading of the mortar is completed. Further, it can be added later to the mortar once kneaded. Either a method of adding the whole amount at a time or a method of adding several times at a time can be adopted.

The mortar composition of the present invention may contain various admixtures and additives in addition to the cementitious material. Examples of these admixtures and additives include, for example, various fiber-based reinforcing materials such as asbestos, glass fiber, polypropylene fiber, vinylon fiber, and aramid fiber, lightweight aggregates such as perlite and vermiculite, blast furnace slag, fly ash, and silica. Examples include fillers such as fume, stone powder, silica sand, etc., expanding agents such as bentonite, surfactants such as water reducing agents, retarders, and early strengtheners (materials).

[0017]

According to the mortar additive of the present invention, while the finishing workability of the mortar can be improved, there is no problem of setting retardation and reduction in strength development. Therefore, the use and construction method of the mortar at the construction site and the like are improved, and problems such as delay of the construction period do not occur. This has a great ripple effect especially in general buildings.

[0018]

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

In the following examples, the degree of substitution of the hydrophobic substituent (A) of the novel polysaccharide derivative of the present invention is determined when the substituent (A) does not have an oxo group at the 1-position (to form an ether). ), The Zeisel method (DGAnderson, Ana
l. Chem., 43, 894 (1971)). When the substituent (A) has an oxo group at the 1-position (forms an ester), the sample is hydrolyzed with an acid. After the addition, esterification was performed with diazomethane, and the amount was determined by gas chromatography. The substitution degree of the substituent (B) was determined by a colloid titration method. That is, a thickener solution having a known concentration was prepared, and an N / 200 methylglycol chitosan solution (known as a colloid titrator, manufactured by Wako Pure Chemical Industries, Ltd.) with a known weight was added thereto with stirring. Several drops of Kojun Pharmaceutical Co., Ltd., for colloid titration) were added. N / 400 polyvinyl potassium sulfate solution (Wako Pure Chemical Industries, Ltd.)
(For colloid titration), and the degree of substitution was calculated from the titer. In the following examples, "degree of substitution" indicates the average number of substituents per constituent monosaccharide residue.

Synthesis Example 1 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP4400, HEC-QP4400, having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl groups of 1.8). Union Carbide) 50g,
A slurry was prepared by adding 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen atmosphere. To this, 4.0 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 7 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of 80% acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours to obtain 49.4 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 80.0 g of isopropyl alcohol and 0.33 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes under a nitrogen stream. To the reaction mixture was added a mixture of 6.4 g of sodium 3-chloro-2-hydroxypropanesulfonate, 2.7 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product
3 times with 500 g of 80% acetone (20% water), and then with acetone 5
After washing twice with 00 g, the mixture was dried under reduced pressure at 70 ° C. for one day to obtain 7.2 g of a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a 3-sulfo-2-hydroxypropyl group (Admixture 1 of the present invention). .

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative is 0.00
The degree of substitution of the 8,3-sulfo-2-hydroxypropyl group was 0.15.

Synthesis Example 2 Hydrophobization was performed in the same manner as in Synthesis Example 1 except that the amount of stearyl glycidyl ether was changed to 8.0 g, and then the amount of sodium 3-chloro-2-hydroxypropanesulfonate was changed.
9.6 g, 2.7 g of 48% aqueous sodium hydroxide solution 4.0 g
Sulfonation was carried out in the same manner as in the above, to obtain a hydroxyethyl cellulose derivative (Admixture 2 of the present invention).

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.01.
The degree of substitution of the 4,3-sulfo-2-hydroxypropyl group was 0.20.

Synthesis Example 3 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Synthesis Example 1 (1), 160 g of isopropyl alcohol and 25% vinyl sulfone were placed in a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. Sodium acid solution 1
8.0 g was charged to prepare a slurry liquid. This was stirred at room temperature for 30 minutes under a nitrogen stream, and then 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and further stirred at room temperature for 60 minutes under a nitrogen stream. Thereafter, the temperature of the slurry liquid was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After the reaction is completed,
The mixture was cooled to 60 ° C., neutralized with acetic acid, and the product was filtered off. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day and night, and hydroxyethyl cellulose derivative substituted with stearyl glyceryl ether group and sulfoethyl group ( Inventive admixture 3) 8.9 g was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative is 0.00
8. The degree of substitution of the sulfoethyl group was 0.18.

Synthesis Example 4 The hydrophobized hydroxyethyl cellulose used in Synthesis Example 2 was sulfonated in the same manner as in Synthesis Example 3 except that the amount of a 25% aqueous solution of sodium vinyl sulfonate was 36.0 g, and substituted with stearyl glyceryl ether group and 2-sulfoethyl group. The obtained hydroxyethyl cellulose derivative (Admixture 4 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative is 0.01.
4. The degree of substitution of the sulfoethyl group was 0.34.

Synthesis Example 5 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Synthesis Example 1 (1), 160 g of 90% isopropyl alcohol and 48 g were placed in a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. 7.2% aqueous sodium hydroxide solution 7.2g
Was added to prepare a slurry liquid, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. After the reaction solution was further cooled to 10 ° C. or lower under ice cooling, 15.0 g of sodium 3-bromopropanesulfonate was charged and stirred at 10 ° C. or lower for 60 minutes. Further, the reaction solution was heated to 80 ° C., and stirred at 80 ° C. for 2 hours to perform sulfonation.
After the completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product is 80% acetone (water 20%) 50
After washing three times with 0 g and then twice with 500 g of acetone,
After drying at 70 ° C. for one day, 8.9 g of a hydroxyethylcellulose derivative (the admixture 5 of the present invention) substituted with a stearyl glyceryl ether group and a 3-sulfopropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.00
The degree of substitution of the 8,3-sulfopropyl group was 0.10.

Synthesis Example 6 (1) A hydroxyethyl cellulose (HEC-QP4400) having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl group of 1.8 was placed in a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. , Union Carbide) 50g,
A slurry liquid was prepared by adding 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen atmosphere. To this, 6.3 g of cetyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. Reaction product 80% acetone
It was washed twice with 500 g and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 50.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
A 500 ml glass separable reaction vessel was charged with 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in (1), 160 g of isopropyl alcohol and 36.0 g of a 25% aqueous solution of sodium vinyl sulfonate to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream. After stirring for 30 minutes, 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and the mixture was further stirred at room temperature under a nitrogen stream for 60 minutes. The slurry liquid was heated to 80 ° C. and stirred at 80 ° C. for 2 hours to perform sulfonation. After the reaction is completed, the reaction solution is
And neutralized with acetic acid and the product was filtered off. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day and night, and hydroxyethyl cellulose substituted with cetyl glyceryl ether group and 2-sulfoethyl group. 8.9 g of a derivative (admixture 6 of the present invention) was obtained.

The substitution degree of the cetyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.016,
The degree of substitution of the sulfoethyl group was 0.35.

Synthesis Example 7 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with methylcellulose having a weight average molecular weight of about 400,000 and a degree of substitution of methyl groups of 1.8 (Metroze SM).
-800, manufactured by Shin-Etsu Chemical Co., Ltd.), 50 g of isopropyl alcohol, and 4.5 g of a 48% aqueous sodium hydroxide solution.
Stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 4.4 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 7 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. 80% reaction product
The resultant was washed twice with 500 g of acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 48.5 g of hydrophobized methyl cellulose.

(2) Equipped with a stirrer, thermometer and cooling pipe
A 500 ml glass separable reaction vessel was charged with 10.0 g of the hydrophobized methylcellulose obtained in (1), 80.0 g of isopropyl alcohol, and 0.33 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid, which was then cooled to room temperature under a nitrogen stream at room temperature. Stirred for minutes. A mixture of 7.7 g of sodium 3-chloro-2-hydroxypropanesulfonate, 3.2 g of a 48% aqueous solution of sodium hydroxide, and 20.0 g of water was added to the reaction solution, followed by sulfonation at 50 ° C. for 8 hours. . After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. 80% product
3 times with 500 g of acetone (20% water), then 500 g of acetone
After drying twice at 70 ° C. under reduced pressure for one day, 8.3 g of a methylcellulose derivative substituted with a stearylglyceryl ether group and a 3-sulfo-2-hydroxypropyl group (Admixture 7 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained methyl cellulose derivative was 0.0075,
The degree of substitution of the 2-hydroxypropyl group was 0.15.

Synthesis Example 8 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 10.0 g of the hydrophobized methylcellulose obtained in Synthesis Example 7 (1) and isopropyl alcohol 160
g and 21.6 g of a 25% aqueous sodium vinyl sulfonate solution to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes. Thereafter, 1.5 g of a 48% aqueous sodium hydroxide solution was charged, and further stirred at room temperature under a nitrogen stream. Stirred for minutes. The temperature of the slurry was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After the completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day and night, and methylcellulose derivative substituted with stearyl glyceryl ether group and 2-sulfoethyl group. (Inventive admixture 8) 9.6 g was obtained.

The degree of substitution of the stearyl glyceryl ether group of the obtained methyl cellulose derivative was 0.0075, and the degree of substitution of the 2-sulfoethyl group was 0.17.

Synthesis Example 9 A 500 ml glass separable reaction vessel equipped with a stirrer, thermometer and cooling tube was charged with 16.2 g of cellulose powder (manufactured by Merck), 250 g of tert-butyl alcohol and 52.0% of a 25% aqueous sodium vinyl sulfonate solution. g was added to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes. Further, 8.0 g of powdered sodium hydroxide was added, and the mixture was stirred at room temperature for 60 minutes. The reaction temperature was raised to 80 ° C, and the mixture was further stirred at 80 ° C for 2 hours to perform sulfonation. After cooling the reaction solution to 60 ° C, water 21.0
g, and further stearyl glycidyl ether 2.4 g
Was added to the mixture, and the mixture was heated to 80 ° C., and stirred at 80 ° C. for 7 hours to perform hydrophobization. After completion of the reaction, the reaction solution was cooled to 60 ° C., acetic acid was added to neutralize excess alkali, and then a cake was obtained by filtration.

The cake obtained is 80% acetone (20% water)
After washing 5 times with 500 g and then 2 times with 500 g of acetone, it was dried under reduced pressure at 70 ° C. for 1 day to obtain 10.3 g of a cellulose derivative substituted with stearyl glyceryl ether group and 2-sulfoethyl group (the admixture 9 of the present invention). Was.

The degree of substitution of the stearyl glyceryl ether group in the obtained cellulose derivative was 0.0070, and the degree of substitution of the 2-sulfoethyl group was 0.53.

Synthesis Example 10 A reaction was carried out in the same manner as in Synthesis Example 9 except that the amount of stearyl glycidyl ether was changed to 4.8 g to obtain a cellulose derivative substituted with a stearyl glyceryl ether group and a 2-sulfoethyl group (the admixture of the present invention). 10) got.

The degree of substitution of the stearyl glyceryl ether group of the obtained cellulose derivative was 0.0130, and the degree of substitution of the 2-sulfoethyl group was 0.53.

Synthesis Example 11 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 1.6 g of 1,2-epoxyoctadecane was added thereto, and the mixture was reacted at 80 ° C. for 7 hours to effect hydrophobicity. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of 80% acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours to obtain 49.4 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 80.0 g of isopropyl alcohol and 0.33 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes under a nitrogen stream. A mixture of 12.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 5.4 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water was added to the reaction solution, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day and night.
7.2 g of a hydroxyethylcellulose derivative (the admixture of the present invention 11) substituted with a hydroxyoctadecyl group and a 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the 2-hydroxyoctadecyl group of the obtained hydroxyethylcellulose derivative was 0.005,3-
The degree of substitution of the sulfo-2-hydroxypropyl group was 0.30.

Synthesis Example 12 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Synthesis Example 11 (1), 160 g of isopropyl alcohol and 25% vinyl were placed in a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube. A slurry liquid was prepared by charging 36.0 g of an aqueous solution of sodium sulfonate. This was stirred at room temperature for 30 minutes under a nitrogen stream, and then 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and further stirred at room temperature for 60 minutes under a nitrogen stream. The temperature of the slurry was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After the reaction is completed,
C., neutralized with acetic acid and the product was filtered off. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day and night.
8.9 g of a hydroxyethylcellulose derivative (admixture 12 of the present invention) substituted with -hydroxyoctadecyl group and 2-sulfoethyl group was obtained.

The degree of substitution of the 2-hydroxyoctadecyl group in the obtained hydroxyethyl cellulose derivative was 0.005,
The degree of substitution of the sulfoethyl group was 0.32.

Synthesis Example 13 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Synthesis Example 11 (1), 160 g of 90% isopropyl alcohol, and 48 g of a hydrophobized hydroxyethyl cellulose obtained in Synthesis Example 11 (1) were placed in a 500-ml separable reaction vessel made of glass equipped with a stirrer, a thermometer, and a cooling tube. 13.1g of aqueous sodium hydroxide solution
Was added to prepare a slurry liquid, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. The reaction solution was further cooled to 10 ° C. or lower under ice cooling, and 30.0 g of sodium 3-bromopropanesulfonate was charged and stirred at 10 ° C. or lower for 60 minutes. Further, the reaction solution was heated to 80 ° C., and stirred at 80 ° C. for 2 hours to perform sulfonation.
After the completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product is 80% acetone (water 20%) 50
After washing three times with 0 g and then twice with 500 g of acetone,
After drying at 70 ° C for one day, the 2-hydroxyoctadecyl group and 3-
8.9 g of a hydroxyethyl cellulose derivative substituted with a sulfopropyl group (Admixture 13 of the present invention) was obtained.

The degree of substitution of the 2-hydroxyoctadecyl group in the obtained hydroxyethyl cellulose derivative was 0.005, 3-
The degree of substitution of the sulfopropyl group was 0.20.

Synthesis Example 14 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 400 g of 88% isopropyl alcohol and 4.7 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 3.6 g of 1-chlorooctadecane was added thereto, and the mixture was reacted at 80 ° C. for 7 hours to effect hydrophobicity. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. Reaction product 80% acetone
It was washed twice with 500 g and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours to obtain 48.7 g of a hydrophobized hydroxyethylcellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 80.0 g of isopropyl alcohol and 0.33 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes under a nitrogen stream. A mixture of 12.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 5.4 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water was added to the reaction solution, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product
3 times with 500 g of 80% acetone (20% water), and then with acetone 5
After washing twice with 00 g, the mixture was dried under reduced pressure at 70 ° C. for one day and night, and a hydroxyethyl cellulose derivative substituted with an octadecyl group and a 3-sulfo-2-hydroxypropyl group (the admixture of the present invention)
14) 8.2 g were obtained.

The degree of substitution of the octadecyl group of the obtained hydroxyethyl cellulose derivative was 0.0030, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.31.

Synthesis Example 15 (1) A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, isopropyl alcohol (800 g) and a 48% aqueous sodium hydroxide solution (3.5 g) were added to prepare a slurry, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. To the reaction mixture was added a mixture of 32.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 17.3 g of a 48% aqueous sodium hydroxide solution and 200 g of water, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product was washed twice with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for 24 hours, and 52 g of a sulfonated hydroxyethyl cellulose derivative was obtained.
I got

(2) Equipped with a stirrer, thermometer and cooling pipe
The sulfonated hydroxyethyl cellulose derivative obtained in (1) 10.0 was placed in a 1000 ml glass separable reaction vessel.
g, 88% isopropyl alcohol 80.0 g and 48% aqueous sodium hydroxide solution 0.73 g to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, stearoyl chloride (0.33 g) was added, and the mixture was reacted at 80 ° C. for 7 hours to hydrophobize. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. 80% acetone (water
20%), washed twice with 100 g and then twice with 100 g of acetone, dried under reduced pressure at 70 ° C. for one day, and dried to obtain a hydroxyethyl cellulose derivative substituted with stearoyl group and 3-sulfo-2-hydroxypropyl group (mixed with the present invention). Agent 15) 8.5 g was obtained.

The degree of substitution of the stearoyl group in the obtained hydroxyethyl cellulose derivative was 0.0048, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.20.

SYNTHESIS EXAMPLE 16 Hydroxyethyl cellulose derivative having a low degree of substitution of stearyl glyceryl ether group was synthesized in the same manner as in Synthesis Example 1 except that the amount of stearyl glycidyl ether was 0.7 g, and hydrophobization was performed. To a stearyl glyceryl ether group and 3-sulfo-2-
A hydroxyethyl cellulose derivative substituted with a hydroxypropyl group (Admixture 16 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.002.
The degree of substitution of the 2,3-sulfo-2-hydroxypropyl group was 0.15.

Synthesis Example 17 In Synthesis Example 1, stearyl glycidyl ether 4.0
g of octyl glycidyl ether and 3.3 g of octyl glycidyl ether, and sulfonation was carried out in the same manner as in Synthesis Example 3 to obtain a hydroxyethyl cellulose derivative having an octyl glyceryl ether group and a 2-sulfoethyl group (the admixture 17 of the present invention). ) Got.

The degree of substitution of the octylglyceryl ether group of the obtained hydroxyethylcellulose derivative was 0.0081,
The degree of substitution of the 2-sulfoethyl group was 0.05.

Synthesis Example 18 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 80
g, 640 g of 80% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 0.84 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then acetone 5
After washing twice with 00 g and drying under reduced pressure at 70 ° C. for one day and night, 72.8 g of a hydrophobized hydroxyethyl cellulose derivative was obtained.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 200 g of 70% isopropyl alcohol and 1.37 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen stream. 3-Chloro-2-
Sodium hydroxypropanesulfonate 4.09g and 48
A 1.7% aqueous solution of sodium hydroxide was added, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is washed once with 340 g of 70% isopropyl alcohol and then with 120 g of isopropyl alcohol
After drying twice at 70 ° C. under reduced pressure for 1 day, 18.3 g of a hydroxyethyl cellulose derivative (admixture 18 of the present invention) substituted with a stearyl glyceryl ether group and a 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0009.
The degree of substitution of the 8,3-sulfo-2-hydroxypropyl group is 0.078.
Met.

Synthesis Example 19 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 80
g, 640 g of 80% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 0.42 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then acetone 5
After washing twice with 00 g and drying under reduced pressure at 70 ° C. for one day, 68.23 g of a hydrophobized hydroxyethyl cellulose derivative was obtained.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 200 g of 70% isopropyl alcohol and 1.37 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen stream. 3-Chloro-2 was added to the reaction mixture.
2.05 g of sodium hydroxypropanesulfonate
Then, 0.86 g of a 48% aqueous sodium hydroxide solution was added, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product was washed once with 340 g of 70% isopropyl alcohol and then twice with 120 g of isopropyl alcohol, dried under reduced pressure at 70 ° C. for 24 hours, and substituted with stearyl glyceryl ether group and 3-sulfo-2-hydroxypropyl group. 17.64 g of a hydroxyethyl cellulose derivative (admixture 19 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0005.
The degree of substitution of the 2,3-sulfo-2-hydroxypropyl group is 0.037
Met.

Synthesis Example 20 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in Synthesis Example 19 (1), 160 g of isopropyl alcohol and 25% vinyl A slurry liquid was prepared by charging 8.3 g of an aqueous sodium sulfonate solution. This was stirred at room temperature under a nitrogen stream for 30 minutes, and then 1.2 g of a 48% aqueous sodium hydroxide solution was charged and stirred at room temperature under a nitrogen stream for 60 minutes. Further, the temperature of the slurry was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration.
The product was washed three times with 170 g of 70% isopropyl alcohol and then twice with 60 g of isopropyl alcohol, and then washed under reduced pressure.
It was dried at 70 ° C. for one day to obtain 8.9 g of a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a 2-sulfoethyl group (Admixture 20 of the present invention).

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0009.
The degree of substitution of the 8,2-sulfoethyl group was 0.082.

Synthesis Example 21 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in Synthesis Example 19 (1), 160 g of 90% isopropyl alcohol and 48 A slurry liquid was prepared by charging 5.4 g of a 5% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. After cooling the reaction solution to 10 ° C or less under ice cooling, sodium 3-bromopropanesulfonate 1
2.0 g was charged and stirred at 10 ° C. or lower for 60 minutes. Further, the temperature of the reaction solution was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product was washed three times with 170 g of 70% isopropyl alcohol and then twice with 60 g of isopropyl alcohol, dried under reduced pressure at 70 ° C. for one day and night, and hydroxyethyl cellulose derivative substituted with stearyl glyceryl ether group and 3-sulfopropyl group ( Inventive admixture 21) 8.9 g was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0009.
The degree of substitution of the 8,3-sulfopropyl group was 0.077.

Synthesis Example 22 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a condenser was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 400 g of 80% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 0.21 g of 1,2-epoxyoctadecane was added, and the mixture was reacted at 80 ° C. for 8 hours to perform hydrophobization. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then with 500 g of acetone.
And dried at 70 ° C. under reduced pressure for one day to obtain 48.8 g of a hydrophobized hydroxyethylcellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry was prepared by charging 100 g of 70% isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 3-Chloro-2-
Sodium hydroxypropanesulfonate 2.1 g and 48
0.88 g of a 10% aqueous sodium hydroxide solution was added, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product is washed three times with 170 g of 70% isopropyl alcohol and then with 60 g of isopropyl alcohol
And dried at 70 ° C. for one day and night under reduced pressure to obtain 7.2 g of a hydroxyethyl cellulose derivative substituted with a 2-hydroxyoctadecyl group and a 3-sulfo-2-hydroxypropyl group (Admixture 22 of the present invention). .

The degree of substitution of the 2-hydroxyoctadecyl group of the obtained hydroxyethyl cellulose derivative was 0.00080,
The degree of substitution of the -sulfo-2-hydroxypropyl group was 0.078.

Synthesis Example 23 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a condenser was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 80
g, 400% of 80% isopropyl alcohol and 3.6 g of 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 0.4 g of 1-chlorooctadecane was added thereto, and the mixture was reacted at 80 ° C. for 8 hours to effect hydrophobicity. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 48.7 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry was prepared by charging 100 g of 70% isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 3-Chloro-2-
Sodium hydroxypropanesulfonate 2.1 g and 48
0.88 g of a 10% aqueous sodium hydroxide solution was added, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is washed three times with 170 g of 70% isopropyl alcohol and then with 60 g of isopropyl alcohol
And dried at 70 ° C. for one day and night under reduced pressure, and a hydroxyethyl cellulose derivative substituted with an octadecyl group and a 3-sulfo-2-hydroxypropyl group (the admixture of the present invention 23)
8.2 g were obtained.

The degree of substitution of the octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.00071, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.080.

Synthesis Example 24 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 70% isopropyl alcohol 500g and 48% sodium hydroxide aqueous solution 3.5g to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 3-chloro to the reaction solution
10.5 g of sodium 2-hydroxypropanesulfonate and 4.4 g of an aqueous sodium hydroxide solution were added, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed three times with 850 g of 70% isopropyl alcohol and then twice with 300 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. for one day to obtain 50.0 g of a sulfonated hydroxyethyl cellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
The sulfonated hydroxyethylcellulose derivative obtained in (1) 10.0 was placed in a 500 ml separable glass reaction vessel.
g, 80.0 g of 88% isopropyl alcohol and 0.01 g of a 48% aqueous sodium hydroxide solution were prepared to prepare a slurry, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. To this, 0.03 g of stearoyl chloride was added, and the mixture was reacted at 80 ° C. for 8 hours to hydrophobize. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed three times with 170 g of 70% isopropyl alcohol and then twice with 60 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. for one day.
8.5 g of a hydroxyethylcellulose derivative substituted with a 1-oxooctadecyl group and a 3-sulfo-2-hydroxypropyl group (Admixture 24 of the present invention) was obtained.

The degree of substitution of the 1-oxooctadecyl group of the obtained hydroxyethyl cellulose derivative was 0.00093, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.081.

Synthesis Example 25 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP4400, HEC-QP4400, having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl groups of 1.8). Union Carbide) 50g,
A slurry was prepared by adding 400 g of 80% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen atmosphere. To this, 0.39 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to effect hydrophobicity. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then with 500 g of acetone.
And dried at 70 ° C. under reduced pressure for 24 hours to obtain 44.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) Equipped with a stirrer, thermometer and cooling pipe
In a 500 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1),
A slurry was prepared by charging 100 g of 70% isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 3-Chloro-2-
2.11 g of sodium hydroxypropanesulfonate and 48
0.88 g of a 10% aqueous sodium hydroxide solution was added, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is washed once with 170 g of 70% isopropyl alcohol and then with 60 g of isopropyl alcohol
After drying twice at 70 ° C. under reduced pressure for one day, 8.8 g of a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a 3-sulfo-2-hydroxypropyl group (mixture 25 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0008.
The degree of substitution of the 1,3-sulfo-2-hydroxypropyl group is 0.079.
Met.

Synthesis Example 26 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP4400, HEC-QP4400, having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl groups of 1.8). Union Carbide) 50g,
A slurry liquid was prepared by adding 400 g of isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 0.7 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic.

(2) After completion of the hydrophobization reaction, the reaction solution was cooled to 40 ° C., 15.8 g of a 48% aqueous sodium hydroxide solution and 24.5 g of sodium monochloroacetate were added, and the mixture was stirred at 40 ° C. for 1 hour, and further stirred at 80 ° C. Carboxymethylation was carried out by reacting at 2 ° C. for 2 hours. After completion of the reaction, the reaction solution was cooled to 60 ° C,
After adding acetic acid to neutralize the excess alkali, the product was filtered off. The product is diluted with 1000 ml of 80% acetone (20% water)
After washing twice with 1000 ml of acetone and drying at 70 ° C. for one day under reduced pressure, 53.4 g of a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a carboxymethyl group (the admixture 26 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.001.
(Hydrophobic substituent content 4.7% by weight), and the degree of substitution of the carboxymethyl group was 0.3.

Comparative Synthetic Example 1 A hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group synthesized in Synthetic Example 1 (1) was used as it was (a degree of substitution of stearyl glyceryl ether group of 0.008) and used as Comparative Admixture 1.

Comparative Synthetic Example 2 The same hydroxyethyl cellulose as used in Synthetic Examples 1 to 6 was sulfonated in the same manner as in Synthetic Example 3 without hydrophobization, and a hydroxyethyl cellulose derivative substituted with a 2-sulfoethyl group ( Degree of substitution of 2-sulfoethyl group 0.18)
(Comparative admixture 2) was obtained.

Comparative Admixture 3 The same hydroxyethylcellulose as used in Synthesis Examples 1 to 6 was used as it was to make Comparative Admixture 3.

Comparative Admixture 4 Carboxymethylcellulose (CMC2280, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight: about 1,000,000, carboxymethylation degree: 0.78) was used as it was to make Comparative Admixture 4.

Comparative Admixture 5 A comparative admixture 5 was prepared using sodium polyacrylate (Carbopol 941, manufactured by Goodrich).

Example With the composition shown in Table 1, cement (manufactured by Chichibu Onoda), sand (standard sand from Toyoura), admixture and water were mixed at 20 ° C. for 3 minutes with a universal mixer (manufactured by Sanei Seisakusho). Thus, a mortar composition was obtained. As the admixture, the above-mentioned admixtures 1 to 26 and comparative admixtures 1 to 5 were used.

[0092]

[Table 1]

The mortar was placed in a steel mold having a length of 30 cm, a width of 30 cm and a depth of 5 cm, and the surface was finished using a trowel. The surface finish was qualitatively confirmed and evaluated as follows. ○: Smooth ironing and good ironing △: Ironing and ironing slightly bad ×: Ironing and ironing bad Mortar composition from mortar composition according to JIS-R5201 Was prepared, and the compressive strength (after 3 days) was measured. The setting time (first time: hour-minute) of these mortar compositions was measured according to ASTM-C403.

The above results are shown in Tables 2 and 3.

[0095]

[Table 2]

[0096]

[Table 3]

From the above results, it can be seen that when the mortar additive of the present invention is used, excellent finishing workability is obtained due to its thickening action, and there is no delay in setting and hardening. On the other hand, in the case of the comparative admixture, there is a problem that a sufficient trowel cannot be obtained, that the setting is delayed and that the strength is reduced.

Claims (7)

[Claims] 1. A polysaccharide or an alkylated or hydroxyalkylated derivative thereof, wherein part or all of the hydrogen atoms of the hydroxyl group are substituted with a hydrophobic substituent (A) having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure. , A sulfonic acid group, a carboxyl group, a phosphoric acid group, a sulfate group, and an ionic hydrophilic substituent (B) containing, as a partial structure, at least one group selected from the group consisting of salts thereof. An additive for mortar, characterized by containing a polysaccharide derivative. 2. The degree of substitution by the hydrophobic substituent (A) is 0.0001 to 1 per constituent monosaccharide residue, and the degree of substitution by the ionic hydrophilic substituent (B) is 0.001 to 2 per constituent monosaccharide residue.
The mortar additive according to claim 1, which is: 3. An alkyl glyceryl ether group having a linear or branched alkyl group having 8 to 40 carbon atoms, or an alkenyl glyceryl having a linear or branched alkenyl group having 8 to 40 carbon atoms, wherein the hydrophobic substituent (A) has 8 to 40 carbon atoms. An ether group or a hydroxyl group, which may be substituted and may have an oxycarbonyl group inserted, and may be a linear or branched alkyl group having 8 to 40 carbon atoms, an alkenyl group or an acyl group, Or more groups, wherein the ionic hydrophilic substituent (B) has 1 carbon atom which may be substituted by a hydroxyl group.
The mortar additive according to claim 1 or 2, which is at least one group selected from the group consisting of a sulfoalkyl group, a carboxyalkyl group, an alkyl phosphate group, and a sulfate ester alkyl group, and salts thereof. 4. The mortar additive according to claim 1, wherein the hydrophobic substituent (A) is an alkyl glyceryl ether group having a linear alkyl group having 12 to 36 carbon atoms. 5. A mortar composition comprising the mortar additive according to any one of claims 1 to 4 and a cementitious material. 6. The mortar composition according to claim 5, further comprising fine aggregate. 7. The mortar composition according to claim 5, wherein the mortar composition is added to the cementitious material in an amount of 0.0001 to 0.03% by weight of the polysaccharide derivative.