JP2010143787A - Admixture for hydraulic composition, and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an admixture for a hydraulic composition in which the blending amount of the mixing agent to a hydraulic substance can be reduced, and which maintains water retainability, operability, surface finishability and pressure-bondability equal to or above those of the conventional one, and in which the regulation of water reducibility and flocculation retardancy is possible as well, and to provide its application. <P>SOLUTION: The admixture for a hydraulic composition comprises: an A component composed of water-soluble cellulose ether in which the viscosity at 20°C in a 1 wt.% aqueous solution is 2,000 to 50,000 mPa s; and a B component composed of sugar having a molecular weight of 90 to 5,000 and/or a derivative thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an admixture for a hydraulic composition mainly used as a building material and its application.

For hydraulic compositions used for building materials, especially plastering materials applied with trowels, it is good at the time of application by adding seaweed glue such as “Tsumata”, a natural product, as an admixture. The workability etc. was ensured. Thereafter, water-soluble cellulose ethers typified by methyl cellulose (water-soluble alkyl cellulose, water-soluble hydroxyalkyl alkyl cellulose, water-soluble hydroxyalkyl cellulose, etc.) were developed as semi-synthetic polymers, and are now generally used.
The following effects (1) to (5) may be mentioned as the effects exhibited in the hydraulic composition containing the water-soluble cellulose ether (hereinafter sometimes simply referred to as cellulose ether).

(1) Neutral to alkaline, can provide a stable and appropriate thickening, and can improve workability at the time of glazing.
(2) Water retention can be improved by a thickening effect and a hydration effect. Improved water retention prevents water from separating from the hydraulic material, for example, and prevents water from evaporating from the hydraulic composition by drying, allowing longer work life when tiling. It becomes.
(3) The pressure-bonding property can be improved by a combination of a thickening effect, improvement in water retention, adhesion of cellulose ether molecules themselves, and the like. For example, it improves the adhesion between the cement mortar, the tile and the base, contributes to preventing the tile from falling off, and contributes to improving the adhesive strength after curing.
(4) Along with improved workability at the time of glazing, the surface finish can be improved.
(5) There is a certain setting delay effect.
An admixture other than cellulose ether has not yet been found that satisfies both the effects (1) to (5) above (particularly improved workability and improved water retention). In spite of the fact that cellulose ether is particularly expensive, there is no substitute in terms of action and effect, so that it must be used.

In recent years, due to remarkable economic growth in China, India, etc., various raw materials have risen in price, and the cost of raw materials and processes has become increasingly urgent even at each building material manufacturer.
Conventionally, as a general method for reducing the cost of a cellulose ether admixture, a higher-viscosity cellulose ether is used to reduce its blending amount, thereby reducing the total cost of the hydraulic composition.

However, in this method, the relationship between the amount of admixture and water retention, and the relationship between the amount of admixture and the thickening effect (workability) are not always the same. If the amount is satisfied, the water retention cannot be satisfied. If the blending amount is adjusted to satisfy the water retention, the viscosity increases excessively and the workability decreases. For this reason, when actually reducing costs, water retention or workability is compromised at the worst.
Many efforts have been made to improve the water retention and workability by adding an auxiliary agent to cellulose ether. For example, Patent Document 1 includes partially anionized polyacrylamide, Patent Document 2 sepiolite, Patent Document 3 hydroxyalkyl starch, Patent Document 4 welan gum and ramsan gum, Patent Document 5 hydroxypropylated starch and Gum or a modified product thereof and Patent Document 6 disclose an approach for improving water retention, workability and the like by combining carrageenan with cellulose ether. In most cases of Patent Documents 1 to 6, it is not directly carried out for the purpose of reducing the blending amount to reduce the cost. However, it is considered that by increasing the water retention, workability, etc., the amount can be reduced by that amount.

The auxiliary agents described in Patent Documents 1 to 6 have a thickening effect independently from the cellulose ether, and the water retention depends only on the cellulose ether. In these methods, when the blending amount of the admixture is adjusted in order to satisfy the water retention, the thickening effect of the auxiliary agent is also manifested and excessively thickened. As a general plastering material, workability deteriorates. Therefore, it is considered that a method different from those described in Patent Documents 1 to 6 is necessary to prepare an admixture for reducing the cost of a versatile hydraulic composition.
Further, it has been thought that even when sugar and / or a derivative thereof used in combination with cellulose ether and used as water retention reinforcement are used alone, water retention is not exhibited.

JP 60-16849 A JP 60-122758 A JP 61-72663 A JP-A-4-367549 Japanese Patent Laid-Open No. 10-36162 JP-A-11-349364

  The object of the present invention is to reduce the blending amount of the admixture with the hydraulic substance while maintaining the same or better water retention, workability, surface finish and pressure-bonding property, and also to adjust the water reduction and setting retardance. It is an object to provide a possible hydraulic composition admixture, a hydraulic material containing the same, a hydraulic composition, and a molded article.

As a result of intensive studies to solve the above problems, the present inventors have surprisingly incorporated an admixture by using a cellulose ether having a higher viscosity than usual and a low molecular type sugar and / or derivative in combination. The present invention was reached after confirming that the water retention, workability and other performances were equal or better despite the fact that the amount was lower than before.
That is, the admixture for hydraulic composition according to the present invention comprises a component A comprising a water-soluble cellulose ether having a viscosity of 2,000 to 50,000 mPa · s at 20 ° C. in a 1% by weight aqueous solution, and a molecular weight of 90 to 5. An admixture for a hydraulic composition comprising 1,000 parts of sugar and / or a B component thereof.

The weight ratio of the A component and the B component (A component / B component) is preferably in the range of 30/70 to 97/3.
The component A is preferably a water-soluble alkyl cellulose, a water-soluble hydroxyalkyl alkyl cellulose, or a water-soluble hydroxyalkyl cellulose.

The hydraulic material concerning this invention is a hydraulic material containing the said admixture for hydraulic compositions and a hydraulic substance.
It is preferable that the hydraulic substance is cement and / or gypsum.

The weight ratio of the admixture for hydraulic composition in the hydraulic material is preferably 0.003 to 2% by weight.
The hydraulic composition concerning this invention is a hydraulic composition formed by mixing the said hydraulic material and water.

  The molded product according to the present invention is a molded product obtained by curing the hydraulic composition.

In the admixture for hydraulic composition of the present invention (hereinafter, sometimes referred to simply as “admixture”), the blending amount with respect to the hydraulic substance can be lowered, and the water retention, workability, and surface finish equivalent to or higher than conventional ones can be reduced. In addition, it retains crimpability. By blending the admixture of the present invention, a hydraulic material that can be further adjusted for water reduction and setting retardance can be obtained.
Since the hydraulic material of the present invention contains the above-mentioned admixture, the blending amount of the admixture with the hydraulic substance can be reduced, and the water retention, workability, surface finish, and pressure-bonding property equal to or higher than those of the conventional material can be maintained. In addition, it is possible to adjust the water-reducing property and the retarding property.

Since the hydraulic composition of the present invention contains the hydraulic material, the blending amount of the admixture with respect to the hydraulic substance can be lowered while maintaining water retention and workability equivalent to or higher than those of conventional ones. It is possible to adjust the water-reducing property and the setting delay property, and it is possible to produce a molded product having a surface finish and pressure-bonding property equal to or higher than those of conventional ones.
Since the molded product of the present invention is obtained by curing the hydraulic composition, the blending amount of the admixture can be reduced while maintaining a surface finish and pressure-bonding property equal to or higher than those of the conventional one.

(Admixture for hydraulic composition)
The admixture for hydraulic composition of the present invention comprises a component A comprising a water-soluble cellulose ether having a viscosity of 2,000 to 50,000 mPa · s at 20 ° C. in a 1% by weight aqueous solution, and a molecular weight of 90 to 5,000. It is an admixture containing B component which consists of saccharide | sugar and / or its derivative (s).

In the present invention, the component A mainly improves the workability by exhibiting an appropriate viscosity increase and contributes to water retention even when used alone, but sufficient water retention is achieved by using it together with sugar and / or its derivatives. It is a component that imparts sex. The component A is not particularly limited as long as it is a water-soluble cellulose ether satisfying a specific physical property of 2,000 to 50,000 mPa · s at 20 ° C. in a 1% by weight aqueous solution. Water-soluble hydroxyalkyl cellulose and water-soluble hydroxyalkyl alkyl cellulose are preferred.
The water-soluble alkyl cellulose is not particularly limited, and examples thereof include methyl cellulose. The water-soluble hydroxyalkyl cellulose is not particularly limited, and examples thereof include hydroxyethyl cellulose and hydroxypropyl cellulose. The water-soluble hydroxyalkylalkylcellulose is not particularly limited, and examples thereof include hydroxypropylmethylcellulose and hydroxyethylmethylcellulose. Among the water-soluble cellulose ethers, water-soluble hydroxyalkylalkylcelluloses such as hydroxypropylmethylcellulose and hydroxyethylmethylcellulose are more preferable.

The water-soluble cellulose ether should just contain at least 1 type in the admixture for hydraulic compositions as A component, and 2 or more types of water-soluble cellulose ether may contain it.
Examples of commercially available water-soluble cellulose ethers include Marporose 90MP-30000, Marporose 90MP-75000, Marporose 90EMP-30000, Marporose 90EMP-75000 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), Metroze 90SH-30000, Metroze 90SH- 100000, Metro's SHV-PF, hi Metro's 90SH-30000, hi Metro's 90SH-100000 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), Meserose PMC-40U, Meserose PMC-50U (above, manufactured by Samsung Precision Chemical Co., Ltd.), etc. Hydroxypropylmethylcellulose; Marporose MX-30000, Marporose ME-250T, Marporose ME-350T (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), Metolose SEB-30T, Metolose SNB-30T, Metolose SNB-60T, Metolose SHV-WF (or, Shin-Etsu Chemical Co., Ltd.) can be mentioned hydroxyethyl cellulose such as.

The viscosity (20 ° C.) of the water-soluble cellulose ether is 2,000 to 50,000 mPa · s, preferably 3,000 to 40,000 mPa · s, when an aqueous solution containing 1% by weight of the water-soluble cellulose ether is used. s, more preferably 4,000 to 36,000 mPa · s, still more preferably 4,000 to 34,000 mPa · s, particularly preferably 8,000 to 30,000 mPa · s, most preferably 8,000 to 22, 000 mPa · s. When the viscosity is lower than 2000 mPa · s, it is necessary to increase the blending amount in order to obtain an appropriate thickening, which may be disadvantageous in cost. On the other hand, when the viscosity is higher than 50,000 mPa · s, there is a large increase in viscosity, and even in combination with the component B, it may be difficult to achieve both water retention and workability. Furthermore, with the current technology, it is very difficult to industrially produce high viscosity cellulose ether, the cost is very high, and it is not economically advantageous.
When the water-soluble cellulose ether is composed of many kinds, even if the viscosity of one kind of water-soluble cellulose ether is outside the range of 2,000 to 50,000 mPa · s, it should be mixed with another water-soluble cellulose ether. Therefore, it may be 2,000 to 50,000 mPa · s as a whole.

The viscosity in the present invention is measured according to JIS Z 8803, and details thereof are described in Examples.
Next, the component B is a component composed of a sugar having a molecular weight of 90 to 5,000 and / or a derivative thereof. In the present invention, the component B is a component that mainly contributes to the effect of improving the water retention function of the component A.

The B component is about 1.0 to 1.1 mPa · s which is very close to water in the viscosity at 20 ° C. of a 1% by weight aqueous solution, and it is considered that no thickening is exhibited even in the hydraulic composition. ing. Although the mechanism of action in the present invention has not been elucidated in detail, the water retention of water-soluble cellulose ether and sugar is not simply summed up, and water-soluble cellulose ether and sugar without water retention have some interaction. It is speculated that the water retention is surprisingly increased.
Examples of sugars include glyceraldehyde; erythrose; threose; ribose; lyxose; xylose; arabinose; arabinose; talose; gulose; glucose; altrose; talose; mannose; galactose; Psicose; fructose; sorbose; tagrose; sucrose; sucrose; lactose; trehalose; neotrehalose; malto-oligosaccharides such as maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, maltoheptaose; isomaltose, panose, Isomalto-oligosaccharides such as isomaltotriose; gentio-oligosaccharides such as gentibiose; nigerose, nigerosyl glucose, Nigero-oligosaccharides such as gelosyl maltose; Cozy-oligosaccharides such as cordobiose; Glycosyl sucrose such as glucosyl sucrose, maltosyl sucrose, maltotriosyl sucrose; Raffinose; stachyose; melezitose; gentianose; lactosucrose; xylosyl fructose; trehalulose; galacto-oligosaccharides such as 4-galactosyl lactose and 6-galactosyl lactose; lactulose; Xylooligosaccharides such as aose and xyloheptaose; cellobiose, cellotriose, cellotetraose, cellopentao Cello-oligosaccharides such as α; cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; cycloinolo-oligosaccharides (such as 6-8 mer); cyclodextran (such as 7-9 mer); Glycosyl-α-cyclodextrin, maltosyl-α-cyclodextrin, galactosyl-α-cyclodextrin, mannosyl-α-cyclodextrin, glycosyl-β-cyclodextrin, maltosyl-β-cyclodextrin, galactosyl-β-cyclodextrin, mannosyl Examples thereof include branched cyclodextrins such as -β-cyclodextrin, glycosyl-γ-cyclodextrin, maltosyl-γ-cyclodextrin, galactosyl-γ-cyclodextrin, and mannosyl-γ-cyclodextrin.

In the present invention, the sugar derivative as the component B means a substance having the same sugar and molecular skeleton, but having a hydroxyl group and / or carbonyl group in the molecule substituted with another substituent.
Examples of sugar derivatives include agarooligosaccharides such as agarobiose, agarotetraose, agarohexaose; N-acetylglucosamine, N-acetylchitooligosaccharide (for example, N-acetylchitobiose, N-acetylchitotri). Aose, N-acetylchitotetraose, N-acetylchitopentaose, N-acetylchitohexaose, N-acetylchitoheptaose, etc.), glucosamine (salt), chitooligosaccharide (salt) (for example, chitobiose, chitotriose, chitotetraose) Aus, chitopentaose, chitohexaose, chitoheptaose, and salts thereof), N-acetylmuramic acid (salt), galactosamine (salt), N-acetylgalactosamine, mannosamine (salt), N-acetylmanno Samin, daunosamine (salt), fruc Samine (salt), hexosamine (salt), ketosamine (salt), muramyl dipeptide (salt), perosamine (salt), neuraminic acid (salt), N-acetylneuraminic acid (salt), N-glycolylneuramin Amino sugars (salts) such as acid (salt), sialic acid (salt), sialic acid oligosaccharide (salt) (for example, N-acetylneuraminyl lactose (salt), N-glycolylneuraminyl lactose (salt), etc.) Gururonic acid (salt), galacturonic acid (salt), uronic acid (salt) such as mannonuronic acid (salt); dimer to 10-mer having glucuronic acid (salt) as a structural unit, mannonuronic acid (salt) as a structural unit 2-10-mer, alginate oligosaccharide (salt) such as 2-10-mer having glucuronic acid (salt) and mannonuronic acid (salt) as structural units; gluconic acid (salt), galactonic acid (salt), Mannon Aldonic acid (salt) such as (salt); Aldaric acid (salt) such as glucaric acid (salt), galactaric acid (salt), mannalic acid (salt); erythritol, maltitol, mannitol, sorbitol, xylitol, lactitol, palatinit Sugar alcohols such as 1,6-anhydroglucose, 3,6-anhydrogalactose, 1,5-anhydrofructose, etc .; methylated β-cyclodextrin, hydroxypropylmethylated β-cyclo Sugar ethers (sugar alkylates, hydroxyalkyl alkylates, carboxyalkylates, hydroxyalkylates) such as dextrin and carboxymethylated β-cyclodextrin (salt); acetylated β-cyclodextrin, sulfated β- Sugar esters such as cyclodextrins (salts) Cetyl iodide, sulfated, phosphorus oxides) and the like.

Among the sugars and / or derivatives (component B), sugars and / or derivatives containing a glucose skeleton in the structural unit are preferable. Preferred B component includes, for example, glucose, sucrose, sucrose, lactose, trehalose, neotrehalose, maltooligosaccharide, isomaltooligosaccharide, gentiooligosaccharide, nigerooligosaccharide, cordierigosaccharide, glycosyl sucrose, fructooligosaccharide, palatinose, raffinose, stachyose, Melezitose, gentianose, lactosucrose, trehalulose, galactooligosaccharide, cellooligosaccharide, cyclodextrin, branched cyclodextrin, N-acetylglucosamine, N-acetylchitooligosaccharide, glucosamine (salt), chitooligosaccharide (salt), glucuronic acid (salt) , Gluconic acid (salt), glucaric acid (salt), maltitol, sorbitol, 1,6-anhydroglucose, methylated β-cyclodextrin, B carboxypropyl methylated -β- cyclodextrin, carboxymethylated -β- cyclodextrin (salt), acetylation -β- cyclodextrin, and the like sulfated -β- cyclodextrin (salt).
The salt in the component B is a pair of ions and sugars and / or derivatives ionized by elimination of protons from acidic groups such as carboxyl groups and sulfate groups in the molecule and / or addition of protons to basic groups such as amino groups. A salt of a sugar and / or a derivative having an ionic bond with a cation or anion.

The pair of cations is not particularly limited, and examples include calcium (Ca ²⁺ ), potassium (K ⁺ ), sodium (Na ⁺ ), and the like. Further, the anion to be paired is not particularly limited. For example, chloride (Cl ⁻ ), sulfuric acid (SO ₄ ²⁻ ), hydrogen sulfate (HSO ₄ ⁻ ), acetic acid (CH ₃ COO ⁻ ), lactic acid ( CH ₃ CH (OH) COO ⁻ ) and the like. The paired cation and anion may further have an ionic bond with one or more cations and anions.
The B component sugar and / or its derivative may contain at least one kind in the admixture for hydraulic composition. Of course, two or more kinds of sugars and / or derivatives thereof may be contained as the B component.

The molecular weight of the component B is 90 to 5,000, preferably 90 to 3,500, more preferably 180 to 3,500, still more preferably 180 to 2,000, and particularly preferably 300 to 2,000. When the molecular weight of component B is greater than 5,000, even when combined with a water-soluble cellulose ether, the water retention is hardly improved, and a large amount needs to be added, which may be disadvantageous in cost.
When the B component is a mixture of a plurality of sugars and / or derivatives thereof, the molecular weight of the B component means a weight average molecular weight and may satisfy 90 to 5,000.

The component B is preferably water-soluble, but can be used without any problem if dissolved in 1 g or more in 100 ml of ion-exchanged water at 20 ° C.
Some B components have a setting delaying action and / or a water reducing action. The setting delaying action is an action that binds to a hydraulic substance, particularly calcium ion, and causes hardening inhibition. Due to the setting delay action, the pot life at the time of construction can be sufficiently secured and the work efficiency can be improved, but in some cases, there is a possibility that the initial strength of the curing may be lowered. The setting retarding action of the component B generally tends to become stronger as the molecular weight becomes smaller or the number of carboxyl groups in the molecule increases, but it is not limited thereto. Although the detailed cause is unknown, it is considered that the three-dimensional structure of the molecule is involved. Water-soluble cellulose ether also has a setting retarding action, and in the present invention, by combining the blending amount / type of water-soluble cellulose ether (A component) with reduced blending amount and sugar and / or its derivative (B component). Compared with the conventional addition of water-soluble cellulose ether, the setting time can be shortened, equalized, or delayed.

The water-reducing action is an action that can be handled with a smaller amount of water since the fluidity of the molded product precursor can be increased by addition. By reducing the amount of water in the molded product precursor, water retention is improved, and it is also possible to improve the press-bonding property. In addition, there is almost no effect on workability after adjusting the amount of water.
The above-mentioned setting retarding action and water reducing action are merely additional actions. If necessary, another setting retarding agent, water reducing agent or setting accelerator, AE water reducing agent, high performance AE may be used as long as the effects of the present invention are not impaired. You may mix | blend a water reducing agent etc.

The weight ratio of the A component and the B component (A component / B component) is preferably 30/70 to 97/3, more preferably 35/65 to 97/3, and still more preferably 40/60. To 97/3, particularly preferably 40/60 to 95/5, most preferably 45/55 to 90/10. When the A component / B component is larger than 97/3, the amount of the admixture is large because it is necessary to add more low-viscosity water-soluble cellulose ether to satisfy the water retention and workability. There may be no advantage over conventional blending. On the other hand, when the A component / B component is smaller than 30/70, moderate thickening cannot be achieved, workability becomes poor, and further, it is difficult to control the setting delay.
[Hydraulic material]
The hydraulic material of the present invention includes the above admixture for hydraulic composition and a hydraulic substance. The hydraulic material of the present invention includes those obtained by separately mixing each component constituting the admixture for hydraulic composition with a hydraulic substance.

As the hydraulic substance, cement and / or gypsum are preferable.
The cement is not particularly limited. For example, ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, low alkali type Portland cement, blast furnace cement, silica cement, fly ash cement, Examples include white Portland cement, ultra-high speed cement, ultra fine particle cement, alumina cement, and jet cement.
The gypsum is not particularly limited, and examples thereof include type I anhydrous gypsum, type II anhydrous gypsum, type III anhydrous gypsum, dihydrate gypsum, α type hemihydrate gypsum, β type hemihydrate gypsum, and the like.

The amount of the hydraulic substance to be blended is not particularly limited as long as the necessary strength is obtained.
The weight ratio of the admixture for hydraulic composition in the hydraulic material is not particularly limited, but is preferably 0.003 to 2% by weight, more preferably 0.003 to 1.5% by weight, More preferably, it is 0.006 to 1.5% by weight, particularly preferably 0.006 to less than 1% by weight, and most preferably 0.006 to 0.8% by weight. When the weight ratio of the admixture for hydraulic composition is larger than 2% by weight, the blending amount is large, which may be disadvantageous in cost. On the other hand, when the weight ratio of the admixture for hydraulic composition is less than 0.003% by weight, performance such as water retention and workability may not be satisfied.

In addition to the above components, the hydraulic material of the present invention is, as necessary, within a range that does not impair the effects of the present invention. For example, the binder, fine aggregate, inorganic filler, organic filler, reinforcing fiber, lightweight Aggregates, expansion materials, adhesion-imparting agents, fillers, rust preventives, waterproofing agents, fungicides, antifoaming agents, setting retarders, setting accelerators, AE agents, AE water reducing agents, high performance AE water reducing agents, etc. Other ingredients such as various admixtures and admixtures can be included.
In addition, synthetic water-soluble polymers such as polyvinyl alcohol, polyalkylene glycol, and polyacrylamide that have been used in combination with water-soluble cellulose ethers, semi-synthetic water-soluble polymers such as hydroxypropylated starch, and natural water-soluble water such as guar gum and welan gum. It is also possible to use a functional polymer in combination as long as the object of the present invention is not impaired. Water-soluble surfactants such as olefin higher fatty acid ester sulfonate, alkylbenzene sulfate ester salt, paraffin sulfate ester salt, and olefin higher fatty acid ester sulfate ester salt that have been used in combination with water-soluble cellulose ether for the purpose of imparting fluidity. An agent may be used in combination as long as the object of the present invention is not impaired.

You may mix the said other component at the time of the admixture for hydraulic compositions as needed.
[Hydraulic composition and molded product]
The hydraulic composition of the present invention is a mixture of the hydraulic material and water.

The amount of water contained in the hydraulic composition is selected according to the type of hydraulic material and the like, and can be a normal dose, but is preferably in the range of 10 to 100% by weight with respect to the hydraulic substance.
The hydraulic composition of the present invention includes those obtained by separately mixing each component constituting the hydraulic material with water.

The molded product of the present invention is obtained by curing the hydraulic composition, for example, concrete base cement mortar, lath base cement mortar, tile cement mortar, sand mortar, fireproof coating cement mortar, plastering Hardened materials such as cement mortar, thick coating cement mortar, repair cement mortar, gypsum plaster, gypsum bond, gypsum putty, etc., are mainly used as building materials.
The molded product is obtained by curing the hydraulic composition by a conventional method.

The present invention is described in detail in the following examples and comparative examples, but the present invention is not limited thereto.
[Measurement of viscosity of each component]
The viscosity in the present invention is a value obtained by using a B-type rotational viscometer as a single cylindrical viscometer at 20 mPa · s or more, and a Canon-Fenske viscometer is used as a capillary viscometer at less than 20 mPa · s. The obtained value. Each viscosity measurement was performed at 20 ° C. according to JIS Z 8803.
When measuring the viscosity using a B-type rotational viscometer, the type and number of rotations of the rotating rotor were determined and measured so that the measured value obtained in% display was within the measurement range of 30 to 80%. The viscosity was obtained by multiplying the measured value by a conversion multiplier under each measurement condition (rotating rotor type / rotational speed). When there are a plurality of measurement condition candidates, they are preferentially adopted in the order of the number of revolutions 12 rpm> 30 rpm> 6 rpm> 60 rpm. 4> No. 3> No. 2> No. Adopted and decided preferentially in order of 1.

According to the above viscosity measurement method, HPMC (1) (hydroxypropylmethylcellulose, 90 type) corresponding to the component A of the present invention was first dissolved in ion-exchanged water at a concentration of 1% by weight, and then the viscosity at 20 ° C. was measured. . The viscosity (measured value) under each measurement condition (rotary rotor type / rotation speed) is No. Out of range at 4/6 rpm (less than 30%), No. 15500 mPa · s (31%) at 4/12 rpm, no. 9,600 mPa · s (48%) at 4/30 rpm, no. 6/400 mPa · s (64%) at 4/60 rpm, no. Out of range (greater than 80%) at 3/6 rpm. Therefore, the measurement conditions are No. 4/12 rpm was adopted, and the viscosity of HPMC (1) was set to 15,500 mPa · s.
In the same manner as the viscosity determination method of HPMC (1), as shown in Table 1, the viscosities of component A, component B, other saccharides and / or derivatives thereof used in Examples and Comparative Examples were determined.

[Example 1]
85 parts by weight of HPMC (1) as mixed species 1 corresponding to component A and β-CD (β-cyclodextrin, molecular weight: 1,150 as mixed species 2 corresponding to component B; manufactured by Nippon Food Chemical Co., Ltd. , Trade name: Celdex B-100) and 15 parts by weight were sufficiently mixed to prepare an admixture for a hydraulic composition. Hereinafter, this admixture for hydraulic composition is referred to as admixture a-1.

[Examples 2 to 10 and Comparative Examples 1 to 13]
In Example 1, admixtures a-2 to 10 were prepared in the same manner as in Example 1 except that the types and amounts of the mixed species 1 and the mixed species 2 were changed as shown in Table 2 or 5. .
As an example of a conventional admixture (comparative admixture) for the admixtures a-1 to 7, HPMC (4) (hydroxypropylmethylcellulose, 90 type) was used as the admixture b-1. Further, as an example of a conventional admixture (comparative admixture) for admixture a-8 to 10, HPMC (5) (hydroxypropyl methylcellulose, 90 type) was used as admixture b-2.

  In Example 1, admixtures c-1 to 11 were prepared in the same manner as in Example 1 except that the types and amounts of the mixed species 1 and the mixed species 2 were changed as shown in Table 3 or 4. . Admixtures c-1 to c-11 are comparative admixtures different from admixture b-1 and admixture b-2.

[Cement mortar test]
Admixtures of types and amounts shown in Tables 6 to 9 with respect to 50 parts by weight of cement (ordinary Portland cement), 25 parts by weight of silica sand No. 5 (fine aggregate) and 25 parts by weight of silica sand No. 6 (fine aggregate) Each was added and mixed well to prepare a hydraulic material.
Next, water was added to the obtained hydraulic material and sufficiently kneaded for 3 minutes with a mortar mixer to prepare cement mortar (hydraulic composition). In addition, kneading | mixing was performed according to the JISR5201 10.4.3 kneading | mixing method. The amount of water added during kneading was adjusted so that the flow value was within the range of 165 to 170 mm by the flow value evaluation described later, and the flow values are shown in Tables 6 to 9. The kneading and the following evaluation and curing were carried out under conditions of a temperature of 18 to 22 ° C. and a humidity of 55% to 75%. Using the prepared cement mortar, the water retention rate evaluation, the glazing workability evaluation, and the tile shift evaluation described later were performed. Furthermore, after curing the cement mortar for one week, the tile adhesive strength evaluation and surface condition evaluation described later were performed using the molded product.

[Gypsum paste test]
In the cement mortar test, instead of cement, silica sand No. 5 and silica sand No. 6, 99 parts by weight of gypsum (α-type hemihydrate gypsum) and 0.20 parts by weight of RS (lignin sulfonic acid, setting retarder) were used, A gypsum paste (hydraulic composition) was prepared and evaluated in the same manner as in the cement mortar test except that the types and amounts of admixtures shown in Table 10 were mixed.
Each evaluation method is described below.

1. Flow value evaluation method: In order to determine the amount of water in cement mortar and gypsum paste in the cement mortar test and gypsum paste test, it was carried out before this test, and the amount of water whose flow value was within the range of 165 to 170 mm was determined according to JIS A 6916. Determined according to
2. Water retention rate evaluation method: According to JIS A 6916 water retention test method (filter paper method), the water spread after 60 minutes and the inner diameter of the ring formwork are measured, and the water retention rate R _w (%) is calculated by the following formula ( Calculated in 1). A high water retention rate indicates that the hydraulic composition has strong water retention, and a low water retention rate indicates poor water retention.
R _w = (L _r / L ₆₀ ) × 100 (1)
(Wherein, _{R w:} water retention rate _{(%), L} 60: 60 minutes after the water spread (mm), _{L r:} ring mold having an inner diameter (mm))

3. Evaluation method of wrinkle coating work: Cement mortar or gypsum paste was applied by wrinkle, and wrinkle elongation, wrinkle slip and wringability were evaluated according to the following criteria (sensory test).
Judgment criteria A: Very good.
○: Good.
Δ: Normal.
X: Bad.
4). Tile displacement evaluation method: Apply a cement mortar with a thickness of 5mm to a concrete plate for sidewalks (JIS A 5304, 300x300x60mm) in a horizontal place, paste a porcelain small-mouth tile, and then add a 200g weight. After mounting and making it vertical, it was held for 60 seconds, and the distance (mm) at which the tile fell during that time was measured.

5). Tile bond strength evaluation method: In the above tile displacement evaluation method, after applying cement mortar with a thickness of 5 mm, a small flat tile was pressure-bonded every elapsed time (immediately, after 30 minutes) with reference to the time when the mortar surface was finished. . Using the molded article after curing for one week, the bond strength for each elapsed time was determined using the Kenken-type adhesive strength tester (manufactured by Yamamoto Uchiki Co., Ltd.) and used as the evaluation result.
6). Surface condition evaluation method: Applying cement mortar or gypsum paste to a concrete plate for sidewalk at a thickness of 5 mm in a horizontal place, curing for one week, and then evaluating the degree of roughness by finger touch observation according to the following criteria did.
Good judgment criteria: Good without roughness.
Defect: Defect with roughness.

[Condensation test]
With the formulations shown in Tables 11 to 13, a hydraulic substance, a setting retarder and an admixture were added and mixed well to prepare a hydraulic material. The weight ratio of the admixture with respect to the hydraulic substance was the same as that in the cement mortar test and the gypsum paste test, so that the comparison was possible regardless of the presence or absence of fine aggregate. Water was added to the hydraulic material and sufficiently kneaded for 2.5 minutes with a mortar mixer to prepare a cement paste or a gypsum paste as a hydraulic composition. The setting test with cement paste was performed according to JIS R 5201. The setting test with gypsum paste was carried out in accordance with JIS A 6904. During kneading, the amount of water added was determined by adjusting the softness as described in each JIS so that the softness was in the range of 6 ± 1 mm for cement paste and 10 ± 1 mm for gypsum paste. . The setting time was evaluated for its start and end. The term “first start” refers to a convenient time in JIS from when water is added to the hydraulic material until the setting of the hydraulic composition starts. Termination refers to the time for convenience in JIS from the addition of water to the hydraulic material until the condensation of the hydraulic composition is completed.
7). Coagulation test method: The test with cement paste was carried out in accordance with JIS R 5201. The test with gypsum paste was performed according to JIS A6904. In each softness test, the amount of water was adjusted so that the softness was 6 ± 1 mm in the case of cement mortar and 10 ± 1 mm in the case of gypsum paste.

[Example A1 and Comparative Example A1]
In Example A1, cement material (50 parts by weight), silica sand No. 5 (25 parts by weight), silica sand No. 6 (25 parts by weight) and admixture a-1 (0.060 parts by weight) were mixed to obtain a hydraulic material. Obtained. Water (19.0 parts by weight) was added to the obtained hydraulic material to prepare a cement mortar. The obtained cement mortar was cured to obtain a molded product. The above evaluation was performed on Example A1. The results are shown in Table 6.
In Comparative Example A1, a hydraulic material was obtained in the same manner as in Example A1, except that the admixture a-1 (0.060 parts by weight) of Example A1 was changed to the admixture b-1 (0.100 parts by weight). A cement mortar and a molding were obtained. As a conventional formulation of Example A1, the above evaluation was performed on Comparative Example A1. The results are shown in Table 6.

In Example A1, although the blending amount of the admixture is smaller than that of Comparative Example A1, the water retention of the obtained cement mortar, the glazing workability, the tile shift, and the tile adhesive strength of the molded product, The surface state was equal to or greater than that of Comparative Example A1. Of the glazing workability, the glazing slip was particularly better than that of Comparative Example A1.
[Examples A2 to A5 and Comparative Examples A2 to A13]
In Examples A2 to A5 and Comparative Examples A2 to A13, the same procedure as in Example A1 was conducted except that the type and amount of the admixture and the amount of water were changed as shown in Tables 6 to 8 in Example A1. A hydraulic material, cement mortar, and a molded product were obtained, and the above evaluation was performed.

In Examples A2 to A5, although the blending amount of the admixture is smaller than that of Comparative Example A1, the water retention rate of the obtained cement mortar, glazing workability, tile displacement, and tile adhesion of the molded product The strength and surface condition were equal to or greater than those of Comparative Example A1. In Example A2, the water reducing action was exhibited, the water retention was further improved, and the tile adhesive strength (particularly at the time of attaching the tile after 30 minutes) was further improved.
In Comparative Example A2, the water retention rate and tile adhesive strength (particularly when tiles were attached after 30 minutes) were poor compared to Comparative Example A1. In Comparative Example A3, the amount of the admixture was increased as compared with Comparative Example A2, so that the workability of wrinkle coating (wrinkle elongation) deteriorated, and excessive thickening was exerted to add more water to match the flow value. Therefore, the water retention was not improved so much. That is, it was not possible to use only a high-viscosity water-soluble cellulose ether as an admixture and reduce the blending amount to exhibit performance equal to or higher than that of conventional blending.

In Comparative Example A4 using only β-CD, which is the B component in the present invention, as an admixture, almost all evaluation results were poor as compared with Comparative Example A1, and in the water retention evaluation, the entire surface of the filter paper was observed within 10 minutes from the start of the test. No spreading water retention was exhibited.
In Comparative Example A5, the water retention rate and tile adhesive strength (particularly when tiles were attached after 30 minutes) were poor compared to Comparative Example A1. In Comparative Example A6, almost all evaluation results such as the water retention rate were poor compared to Comparative Example A1. However, Comparative Example A6 was slightly better than Comparative Example A4. That is, β-CD alone was inferior in water retention even when compared to methyl cellulose having a low molecular weight (weight average molecular weight: 85,000) alone.

In Comparative Example A7, the water retention rate and tile adhesive strength (especially when tiles were attached after 30 minutes) were poor compared to Comparative Example A1, and lignin sulfonic acid used as a setting retarder for gypsum was combined with a highly viscous water-soluble cellulose ether. Even when used in combination, the effect of the present invention was not observed.
In Comparative Examples A8 to A11, carrageenan (iota carrageenan sodium salt) was used instead of the sugar and / or derivative of component B, but the performance of Comparative Example A1 could not be satisfied. In Comparative Example A8 and Comparative Example A10, the water retention rate and tile adhesive strength (particularly when tiles were attached after 30 minutes) were poor compared to Comparative Example A1. In Comparative Example A9 and Comparative Example A11, in addition to reducing the amount of water-soluble cellulose ether that maintained water retention, excessive thickening due to the increase in the amount of carrageenan was exhibited, and the flow value was increased. The water retention and tile adhesion strength (especially when tiles were attached after 30 minutes) were drastically reduced. Furthermore, of the cocoon coating workability, the cocoon elongation was poor.

  Also in Comparative Example A12 and Comparative Example A13, the water retention rate and tile adhesive strength (particularly when tiles were attached after 30 minutes) were poor compared to Comparative Example A1. That is, even when HP-starch (hydroxypropyl starch, hydroxypropyl group average substitution degree: 0.8) or welan gum is used in place of the sugar and / or derivative of component B, it does not satisfy the performance of Comparative Example A1. could not.

註 1) Spread over the entire filter paper within 10 minutes of the start of the test.
註 2) Slide off from the pasting surface.

[Example A6 and Comparative Example A14]
In Example A6, cement (50 parts by weight), silica sand No. 5 (25 parts by weight), silica sand No. 6 (25 parts by weight) and admixture a-8 (0.105 parts by weight) were mixed to obtain a hydraulic material. Obtained. Cement mortar was prepared by adding water (20.0 parts by weight) to the obtained hydraulic material. The obtained cement mortar was cured to obtain a molded product. The above evaluation was performed on Example A6. The results are shown in Table 9.
In Comparative Example A14, the admixture a-8 (0.105 parts by weight) of Example A6 was changed to the admixture b-2 (0.175 parts by weight), and the amount of water was changed from 20.0 parts by weight to 21.21 parts by weight. A hydraulic material, cement mortar, and molded product were obtained in the same manner as in Example A6 except that the amount was changed to 0 part by weight. As a conventional formulation of Example A6, the above evaluation was performed on Comparative Example A14. The results are shown in Table 9.

In Example A6, although the blending amount of the admixture is smaller than that of Comparative Example A14, the water retention of the obtained cement mortar, the glazing workability, the tile shift, and the tile adhesive strength of the molded product, The surface condition was equal to or greater than that of Comparative Example A14. Of the glazing workability, the glazing slip was particularly good as compared with Comparative Example A14. Furthermore, the water reducing action was exhibited, the water retention was further improved, and the tile adhesive strength (particularly when the tile was attached after 30 minutes) was further improved.
[Examples A7 and A8]
In Examples A7 and A8, the hydraulic material, cement mortar, and cement mortar were changed in the same manner as in Example A6 except that the type and amount of the admixture and the amount of water in Example A6 were changed as shown in Table 9. Each molded product was obtained and evaluated.

  In Examples A7 and A8, although the blending amount of the admixture was smaller than that in Comparative Example A14, the water retention rate of the obtained cement mortar, glazing workability, tile displacement, and tile adhesion of the molded product The strength and surface condition were equal to or greater than those of Comparative Example A14. In Example A7, the water-reducing effect was exhibited, the water retention was further improved, and the tile adhesive strength (particularly at the time of attaching the tile after 30 minutes) was further improved.

[Example B1 and Comparative Example B1]
In Example B1, gypsum (99 parts by weight), RS (0.20 parts by weight) and admixture a-1 (0.36 parts by weight) were mixed to obtain a hydraulic material. Water (34.5 parts by weight) was added to the obtained hydraulic material to prepare a gypsum paste. The obtained gypsum paste was cured to obtain a molded product. The above evaluation was performed on Example B1. The results are shown in Table 10.
In Comparative Example B1, the admixture a-1 (0.36 parts by weight) of Example B1 was changed to the admixture b-1 (0.60 parts by weight), and the amount of water was changed from 34.5 parts by weight to 35 parts. A hydraulic material, a gypsum paste, and a molded product were obtained in the same manner as in Example B1 except that the amount was changed to 5 parts by weight. As a conventional formulation of Example B1, the above-described evaluation was performed on Comparative Example B1. The results are shown in Table 10.

In Example B1, although the blending amount of the admixture is smaller than that in Comparative Example B1, the water retention rate of the obtained gypsum paste, the wiping workability, and the surface state of the molded product are comparative examples. It was equal to or better than B1. Of the glazing workability, the glazing slip was particularly good as compared with Comparative Example B1.
[Examples B2 and B3]
In Examples B2 and B3, the hydraulic material, the gypsum paste, and the mixture of Example B1 were changed in the same manner as in Example B1, except that the type and amount of the admixture and the amount of water were changed as shown in Table 10. Each molded product was obtained and evaluated.

  In Examples B2 and B3, although the blending amount of the admixture is smaller than that in Comparative Example B1, the water retention rate of the obtained gypsum paste, the coating workability, and the surface state of the molded product are It was equal to or greater than Comparative Example B1.

[Example C1 and Comparative Example C1]
In Example C1, cement (50 parts by weight) and admixture a-1 (0.060 parts by weight) were mixed to obtain a hydraulic material. Water (14.5 parts by weight) was added to the obtained hydraulic material to prepare a cement paste. The above evaluation was performed on Example C1. The results are shown in Table 11.
In addition, the mixing | blending of the hydraulic material of Example C1 is mixing | blending except the fine aggregate among the mixing | blendings of Example A1, and the weight ratio of the admixture with respect to a hydraulic substance corresponds with no change. Example C1 shows an indication of the setting time of Example A1.

In Comparative Example C1, water was changed in the same manner as in Example C1, except that the admixture b-1 (0.100 parts by weight) was changed to the admixture a-1 (0.060 parts by weight) of Example C1. Hard materials and cement paste were obtained. As a conventional formulation of Example C1, the above evaluation was performed on Comparative Example C1. The results are shown in Table 10. Comparative example C1 shows a measure of the setting time of comparative example A1.
The setting time of Example C1 was delayed by about 1 hour as compared with Comparative Example C1, which is a conventional formulation, as shown in Table 11, but the setting was almost the same.

[Examples C2 to C5]
In Examples C2 to C5, the hydraulic material and cement paste were changed in the same manner as in Example C1 except that the type and amount of the admixture and the amount of water in Example C1 were changed as shown in Table 11. Each was obtained and evaluated. Examples C2 to C5 show the guidelines for the setting times of Examples A2 to A5, respectively.
As shown in Table 11, the setting time in Examples C2 to C5 can be 10 minutes earlier, 75 minutes slower, or 40 minutes faster at the end, as shown in Table 11. It was possible to delay about 3 hours.

[Examples C6 to C8 and Comparative Example C2]
In Examples C6 to C8 and Comparative Example C2, a hydraulic material and a cement paste were obtained in the same manner as in Example C1 except that the type and amount of the admixture and the amount of water were changed as shown in Table 12. The above evaluation was conducted. In Examples C6 to C8, Comparative Example C2 was a conventional formulation. Examples C6 to C8 and Comparative Example C2 show guidelines for the setting times of Examples A6 to A8 and Comparative Example A14, respectively.
Also in Examples C6 to C8, as shown in Table 12, it was possible to adjust the setting time as compared with Comparative Example C2, which was a conventional formulation.

[Examples C9 to C11 and Comparative Example C3]
In Examples C9 to C11 and Comparative Example C3, water was used in the same manner as in Example C1, except that the type and amount of hydraulic substance, the type and amount of admixture, and the amount of water were changed as shown in Table 13. A hard material and a gypsum paste were obtained, and the above evaluation was performed. In Examples C9 to C11, Comparative Example C3 was a conventional formulation. Examples C9 to C11 and Comparative Example C3 show the guidelines for the setting times of Examples B1 to B3 and Comparative Example B1, respectively.
Also in Examples C9 to C11, as shown in Table 13, it was possible to adjust the setting time as compared with Comparative Example C3, which is a conventional formulation.

In any of the above tables, the following abbreviations are used.
HPMC (1): hydroxypropylmethylcellulose HPMC (2): hydroxypropylmethylcellulose HPMC (3): hydroxypropylmethylcellulose HPMC (4): hydroxypropylmethylcellulose HPMC (5): hydroxypropylmethylcellulose HEMC: hydroxyethylmethylcellulose β-CD: β -Cyclodextrin (Molecular weight: 1,150, manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: Celdex B-100)
Lactosucrose: Lactosucrose (Molecular weight: 504, manufactured by Shisui Minato Sugar Co., Ltd., trade name: lactose oligo LS-90P)
Glucose: Glucose (Molecular weight: 180, manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: solar eclipse hydrous crystal glucose # 50)
Gluconic acid: Sodium gluconate (Molecular weight: 198, manufactured by Nagase ChemteX Corporation, trade name: GL-P)
Mannitol: Mannitol (Molecular weight: 182; manufactured by Kao Corporation, trade name: Mannitol Kao)
MC: methylcellulose (weight average molecular weight: 85,000)
RS: Lignin sulfonic acid (setting retarder)
Carrageenan: iota carrageenan sodium salt HP-starch: hydroxypropyl starch (hydroxypropyl group average substitution degree: 0.8)
Welan gum: Welan gum cement: Ordinary Portland cement Silica sand No. 5: Fine aggregate Silica sand No. 6: Fine aggregate gypsum: α type hemihydrate gypsum

Claims (8)

  A component composed of a water-soluble cellulose ether having a viscosity of 2,000 to 50,000 mPa · s in a 1% by weight aqueous solution at 20 ° C., and a B component composed of a sugar having a molecular weight of 90 to 5,000 and / or a derivative thereof. An admixture for a hydraulic composition, comprising:   The admixture for hydraulic compositions according to claim 1, wherein a weight ratio of the A component and the B component (A component / B component) is in the range of 30/70 to 97/3.   The admixture for hydraulic composition according to claim 1 or 2, wherein the component A is at least one selected from water-soluble alkylcellulose, water-soluble hydroxyalkylalkylcellulose, and water-soluble hydroxyalkylcellulose.   The hydraulic material containing the admixture for hydraulic compositions in any one of Claims 1-3, and a hydraulic substance.   The hydraulic material according to claim 4, wherein the hydraulic substance is cement and / or gypsum.   The hydraulic material of Claim 4 or 5 whose weight ratio of the said admixture for hydraulic compositions which occupies for the said hydraulic material is 0.003 to 2 weight%.   The hydraulic composition formed by mixing the hydraulic material and water in any one of Claims 4-6.   A molded product obtained by curing the hydraulic composition according to claim 7.