JP3342647B2 - Additive for gypsum adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for a gypsum-based adhesive excellent in adhesiveness, and a gypsum-based adhesive composition containing the additive. More specifically, the present invention relates to an additive for a gypsum-based adhesive and an adhesive composition that can improve the base adhesion of a gypsum molded article, using a cementitious material such as hemihydrate gypsum as a main raw material.

[0003]

2. Description of the Related Art Gypsum boards (plaster plaster boards) such as plaster wall boards and gypsum laths, and gypsum blocks are soundproof,
It is widely used for ceilings, partitions, walls, etc. as a building material having heat insulation, fire resistance, and the like. In particular, gypsum board has been rapidly spread in recent years because it has the convenience that it can be directly used as a ceiling material, wall material, partition material, or the like by bonding to a base material.

When a gypsum board is constructed on site, water is added to a gypsum-based adhesive and kneaded, and a base material such as wood such as veneer, slate, metal, or glass is applied with a trowel, and then the gypsum board Is performed. Here, the gypsum-based adhesive refers to a cementitious material such as hemihydrate gypsum (calculated gypsum) as a main raw material to which a water-soluble polymer or the like is blended. Gypsum-based adhesives have the advantage that they are well compatible with gypsum boards and the like and are easy to handle.

[0005]

However, the gypsum-based adhesive has a property that its own weight is large due to its material. Therefore, for example, when a ceiling or a wall is constructed, there is a problem that the adhesiveness to a base material is not always good. Therefore, conventionally, to improve the adhesiveness, cellulose derivatives such as methylcellulose, hydroxymethylcellulose, and carboxymethylcellulose have been used to impart plasticity and adhesiveness to the water-kneaded product of gypsum, but the effect is still insufficient. At present, it is not enough and improvement is desired. Therefore, an object of the present invention is to provide an additive capable of providing a gypsum-based adhesive having excellent base adhesion, and a gypsum-based adhesive composition thus obtained.

[0006]

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. Polysaccharide derivatives obtained by substitution with an ionic hydrophilic group such as show a large thickening effect even in a very small amount under strong ionic strength, when this is used as an additive for gypsum-based adhesives, such as gypsum board The gypsum molding was found to be extremely excellent in base adhesion. The present invention has been completed based on this finding.

That is, the present invention relates to a hydrophobic substituent (partially or completely) in which a part or all of the hydrogen atoms of the hydroxyl group of a polysaccharide or an alkylated or hydroxyalkylated derivative thereof have 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. A gypsum-based adhesive additive comprising a substituted polysaccharide derivative. Further, the present invention also provides a gypsum-based adhesive composition containing such an additive together with a cementitious material.

[0008]

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 phosphoric acid 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.

[0010] These polysaccharide derivatives according to the present invention have different solubility in kneading water and a higher viscosity 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 adhesiveness can be given to a gypsum-based adhesive. From these viewpoints, the hydrophobic substituent (A)
Is from 0.0001 to 1 per unit of the constituent monosaccharide residue.
And 0.0005 to 0.01 is more preferable. The degree of substitution by the ionic polar substituent (B) is 0.001 to 2 per unit of the constituent monosaccharide residue, and more preferably 0.01 to 1. Particularly preferred substitution degree is 0.0007 to 0.00 for the hydrophobic substituent (A).
5, and the ionic hydrophilic substituent (B) is 0.02 to 0.15.

In the present invention, the 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 group-substituted products 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 is characterized in that a hydrogen atom of a hydroxyl group of a polysaccharide or an alkylated or hydroxyalkylated derivative thereof is partially hydrophobized (introduction of a hydrophobic substituent (A)) or hydrophilized (hydrophobic substituent (A)). 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 gypsum-based adhesive additive of the present invention containing the above polysaccharide derivative is added includes:
It is an inorganic substance that shows curability when kneaded with water, and a typical example is hemihydrate gypsum (plaster of Paris), but is not limited thereto. Note that hemihydrate gypsum is generally obtained by sintering natural gypsum, phosphate gypsum, titanium gypsum, flue gas desulfurization gypsum, etc. at 110 to 120 ° C.

In the present invention, the amount of the gypsum-based adhesive additive added to the cementitious material depends on the desired thickening,
It can be appropriately determined according to the degree of adhesion, for example, for the cementitious material, the above-mentioned polysaccharide derivative is 0.0001
~ 0.03% by weight is preferable, and 0.0005 ~ 0.
01% by weight is preferable from the viewpoint of the balance between adhesiveness 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 a powder, and its addition time is determined by dry blending with cementitious materials,
It may be before kneading the gypsum-based adhesive, such as dissolving in kneading water, or during the kneading period of the gypsum-based adhesive, i.e., simultaneously with or immediately after water injection into the cementitious material, from the end of kneading the gypsum-based adhesive. It is also possible to add during. Further, it can be added later to the gypsum adhesive 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 adhesive composition of the present invention may contain various admixtures and additives in addition to the cementitious material. As these admixtures and admixtures, for example,
Various fibrous reinforcing materials such as asbestos, glass fiber, polypropylene fiber, vinylon fiber and aramid fiber; lightweight aggregates such as perlite and vermiculite; fillers such as blast furnace slag, fly ash, silica fume, stone powder, silica sand, etc.
Swelling agents such as bentonite, surfactants such as water reducing agents,
Delaying agents, early-strength agents (materials) and the like can be mentioned.

[0018]

According to the gypsum-based adhesive additive of the present invention, the adhesion of the gypsum-based adhesive to the base can be improved. The method is improved, especially in general buildings, and its ripple effect is great.

[0019]

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 hydroxyethyl cellulose (HEC-QP4400, 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 cooling tube. 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 was 0.00
The degree of substitution of the 8,3-sulfo-2-hydroxypropyl group was 0.15.

Synthesis Example 2 Hydrophobization was carried out 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 reduced.
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 of the obtained hydroxyethyl cellulose derivative is 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 hydroxyethyl cellulose 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 cooling tube. 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 was 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 according to Synthesis Example 3 with the amount of a 25% aqueous solution of sodium vinyl sulfonate being 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 separable glass reaction vessel equipped with a stirrer, a thermometer, and a cooling tube. 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 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (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 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 of 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 in 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 stearyl glyceryl ether group in the obtained cellulose derivative was 0.0070, and the degree of substitution of 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, and 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 in 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 in 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 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 hydroxyethylcellulose obtained in Synthesis Example 11 (1), 160 g of 90% isopropyl alcohol, and 48 g of the hydrophobized hydroxyethyl cellulose obtained in Synthesis Example 11 (1) were placed in a 500-ml glass separable reaction vessel 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 hydroxyethylcellulose 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 in 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) In a 1000 ml glass separable reaction vessel equipped with a stirrer, thermometer and cooling tube, 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 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, 0.42 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-
2.05 g of sodium hydroxypropanesulfonate and 48
0.86 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 340 g of 70% isopropyl alcohol and then with 120 g of isopropyl alcohol
After drying twice at 70 ° C. under reduced pressure for one day, 17.64 g of a hydroxyethylcellulose derivative (admixture 19 of the present invention) substituted with stearyl glyceryl ether group and 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0005.
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 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in Synthesis Example 19 (1), 160 g of 90% isopropyl alcohol and 48 g 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 lower under ice cooling, sodium 3-bromopropanesulfonate 12.0 g
And stirred at 10 ° C. or lower for 60 minutes. In addition, the reaction solution
The temperature 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 is washed three times with 170 g of 70% isopropyl alcohol and then with 60 g of isopropyl alcohol.
g, and dried at 70 ° C. for one day and night under reduced pressure to obtain a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a 3-sulfopropyl group (the admixture of the present invention).
21) 8.9 g were 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 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 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, thermometer and 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, 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. under reduced pressure 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 23)
8.2 g were obtained.

The substitution degree of the octadecyl group of the obtained hydroxyethyl cellulose derivative was 0.00071, and the substitution degree 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 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, 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 hydroxyethylcellulose derivative was 0.00093, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.081.

Synthesis Example 25 (1) A hydroxyethyl cellulose (HEC-QP4400, 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 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, thermometer and cooling tube 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 the completion of the hydrophobizing 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 was 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 as 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, hemihydrate gypsum, admixture and water were mixed at 20 ° C. for 1 minute with a universal mixer (manufactured by Sanei Seisakusho) to obtain an adhesive composition. As the admixture, admixture 1 shown above was used.
-26 and comparative admixtures 1-5.

[0093]

[Table 1]

Gypsum board (9 mm thick) was cut into 50 cm × 50 cm pieces, and the adhesive composition obtained above was uniformly and quickly applied on one side, and then pressed 1 m below the vertical plywood plate. To observe the presence or absence of shear drop.
The same evaluation was repeated five times, and the evaluation was made out of 50 points according to the following criteria.

No shear drop-10 points Less than 10 cm shear drop-5 points More than 10 cm shear drop-0 points The results are shown in Tables 2 and 3.

[0096]

[Table 2]

[0097]

[Table 3]

From the above results, it can be seen that when the gypsum-based adhesive additive of the present invention is used, excellent base adhesion can be obtained due to its thickening action. On the other hand, in the case of the comparative admixture, sufficient base adhesiveness cannot be obtained, and it is insufficient as a gypsum-based adhesive such as gypsum board.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-301901 (JP, A) JP-A-62-83347 (JP, A) JP-A-55-75955 (JP, A) US Patent 4,845,207 (US) U.S. Pat. No. 4,784,963 (US, A) European Patent Application Publication No. 362769 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C04B 24/38

Claims (6)

(57) [Claims] Claims: 1. A polysaccharide or an alkylated or hydroxyalkylated derivative thereof, wherein a part or all of the hydrogen atoms of the hydroxyl group is a hydrocarbon chain having 8 to 40 carbon atoms (a phenethyl group and a phenethyl group).
A hydrophobic substituent (A) having a partial structure ( excluding 2-ethylhexyl group ), a sulfonic acid group and a carboxyl group
Ionic hydrophilic substituent containing one or more groups selected from the group consisting of salts to the parallel beauty as a partial structure (B)
An additive for a gypsum-based adhesive, characterized by containing a polysaccharide derivative substituted with: 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 additive for a gypsum-based adhesive 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 gypsum-based adhesive 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. Additive. 4. The gypsum-based adhesive 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 gypsum-based adhesive composition comprising the gypsum-based adhesive additive according to claim 1 and a cementitious material. 6. The gypsum-based adhesive composition according to claim 5, wherein the gypsum-based adhesive composition is added to the cementitious material in an amount of 0.0001 to 0.03% by weight of the polysaccharide derivative. [0001]