WO2010016618A1

WO2010016618A1 - Water-reducing agent for hydraulic compositions

Info

Publication number: WO2010016618A1
Application number: PCT/JP2009/064283
Authority: WO
Inventors: 藤田修一; 大久保真; 濱井利正; 名嘉良仁
Original assignee: 花王株式会社
Priority date: 2008-08-08
Filing date: 2009-08-06
Publication date: 2010-02-11
Also published as: JP5536389B2; JP2010059045A; CN102112411A; CN102112411B; MY164839A

Abstract

A water-reducing agent for hydraulic compositions, containing a naphthalenesulfonic acid-formaldehyde condensate which has a weight-average molecular weight of 1,900 to 24,000 as determined by GPC and in which the peak area of molecular weight of 4,000 or below as determined by GPC is 17 to 38% of the whole peak area as determined thereby.

Description

Mysterious

Rigid water reduction field

This relates to water reduction for hydraulic use.

Coming

It is a chemistry used to improve the hardness by reducing the amount required to obtain the required slump by dispersing the cementitious cement. In the past, the performance of talen-based (naphthalene hon formaldehyde compound) lamin-based melamine sulphone formaldehyde compound has been known.

JP A6 34 045 9 There are several proposed fluidity retention techniques for strikes, slurries, mortars, concrete, etc., using cement gypsum as a hydraulic material in systems that use or can be used. JP 7 0 9 5 8 JP 7 247 47 JP 63 5 346. For example, JP A6 340459 JP A7 0 95 58 JP 7 describes a combination of thalene or its conductor and formaldehyde-functional material and its conductor. Among these, tarens phonon formaldehyde compound is a cement compound based on its salt, and as a particularly effective fluidity retention technique, a polymer compound with lower fin ethylene saturated dicarbonate (water rain) and water reduction is used as a cement compound. There is a method to prevent the collection of cement by using (J P 63 5 346 o

1) The weight average numerator obtained by the LPC is as follows: 1 200 to 2400 0, and the Pita product under the molecule 4 0 0 0 obtained by the GPC is This relates to water reduction for hydraulic use, which contains tarens hon formaldehyde compound, which is 7 to 3 in total.

, R is a hydrogen atom and alkyl having 4 to 4, is a condensation, and the above number. Represents an ion. () Is a hydrogen atom.

Tarenshon Primer Formaldehyde 0 · 6 to 097 is set to 4 to 5 at 8 5 9 5 C and 4 to 30 at 0 to h for Talensphone having an alkyl group of prime number ~ 4 The method relates to the above-mentioned water reduction method for rigidity, which has a step of neutralizing.

In addition, it has the above-mentioned structure and is a permeation chromatography (weight-average molecular weight obtained by GPC standard 8700-2 9 And 300 steps of mixing the 300 talens hon formaldehyde compound with the above 1) structure and the tarescence hon formaldehyde compound having a weight average molecular weight of 900 to 4,000 obtained by LPC. It relates to the above-mentioned water reduction method for hardness.

Further, the present invention relates to a hydraulic method having a step of mixing the above-mentioned water reduction for hardness, a hydraulic substance and water by any of the following methods (1 to 3).

() Add water to hard material at the same time

Method 2) Add to hard water

Method (3) Add after the hard substance is finished and before it is mixed

In addition, the weight average molecule 900 to 2400 obtained by the above-mentioned (1) structure and obtained by Lumper Tomography GPC) is obtained, and the pixel product under the molecule 400 obtained by GPC is all pixels. This is a water-reduction process for the hardness of tarens hon formaldehyde compounds that are 7 to 3 8. Detailed explanation

Talence phon formaldehyde compounds are usually used for water reduction with a weight average molecular weight of 8000 to 0, but they have the title of hydraulic slump loss.

As a method to improve the quality, it is common to add a delay such as glucocon soda. The limited flow cannot be maintained. JP B6 3 5 3 6 is said to be effective for the slump loss result, but further improvement in strength (especially in the initial stage) is desired. In addition, it is advantageous for JP A6 3 to contain industrially, but if it is not used in a state where it does not settle, the designed thrompros results will not be produced. Means to keep the powder in place A means that can be pulverized before use is required.

The present invention provides a talen system that can impart excellent results and strength development results to hydraulic properties such as strikes, slurries, mortars, and contaminants using cement gypsum as a hydraulic substance.

According to Ming, it is possible to provide hydraulic water loss that is excellent in the flow of streaks, slurries, mortars, contaminants, etc. with cement gypsum as a hydraulic substance and excellent in the degree of hardening.

The preferred embodiment of the present invention has the structure of the above-mentioned), and a tarenshon formaldehyde compound (below, high S) having a weight average molecular weight of 8700 to 293 300 obtained by the specification of lupachromatography GPC). 1), and blended with a tarenshon formaldehyde compound (below, low S) having a weight average molecular weight of 90 to 4,000 obtained by rupermint rotograph (GPC) determination, As described above, which is water reduction for hardness, S and S compound

More preferably, the SS is 80 2 0 to 2 0 80. In addition, in the above, S is the total Pita product of 2 to O under the molecule 4 obtained by GPC constant, and the total Pita product of 4000 under the SG constant is 3 to 8 Even more preferably.

Talence phon formaldehyde compound according to light below, S is represented by weight average molecular weight 900-24,000, preferably 900-0970, more preferably 900-600, and more preferably 900-0-4 , 00. In addition, the molecular weight obtained under G 400 is sometimes 7 to 38, preferably from 7 to 38, more preferably from 3 to 3 in terms of fluidity. 3 From the viewpoint of fruit and initial degree of fruit, it is preferably 20 to 3, more preferably 2 to 33, and still more preferably 27 to 33. In this case, it is a standard for flowability and strength development performance, and this ratio is in the above range, meaning that it has a certain amount of the corresponding product. In addition, the term “S” includes those in which all of the tarens phone formaldehyde compound is a salt.

Here, the average molecular weight and pita of S were measured by the following permeation chromatography GPC method. It is assumed that it was derived based on the average molecular weight of S and the pita and coal pita in Ming. That is, the sum derived from the P pit mass under 4000 weight average molecules detected after the standard 4000 for the total P pit derived from S. Physically, it includes a pioneer containing 3 of the thalens phonon formaldehyde compound, 2, 4 derived from talenediphonic acid and talenmonophonic acid. Sum the products.

GPC WX G WX ()

3 0 C COO a C C 6 4

0 7

V28 0

Sample size 0 2 1

Stock Polystyrene Phone Soda (Uniform Molecule 4 8 00 0 8 0 0 0 3 5 00 0 88 00 0 7 8 0 00 0)

V 8020 Corporation

Pita derived from Pita quality below 4000 Pita Pita derived from Pita quality exceeding 400 000 GPC 8020 Luchi Station 8020

GPC Data Application Ve so 2011

Copy g C) 19971999

With regard to the average molecular weight and the P-filled S, in (), the above-mentioned Pita-filled one can be obtained relatively easily by reacting with ordinary tarensphone formaldehyde. On the other hand, the polymer () tends to be difficult to obtain a material satisfying the above-mentioned Pita in response to the usual talens phone formaldehyde. Therefore, it is preferable from the viewpoint of workability that the S related to light is obtained by mixing S with known molecular weight and distribution. For example, GPC The weight average molecular weight is preferably 000-000 degrees

In S, for example, Strain (b) 50, weight average molecular weight is preferably 200 to 3,500 degrees S (for example, Strain, Demol R, Demol R) So you can get SF related to Ming. Also these

A method of synthesizing and mixing S S with each other is also preferable.

Therefore, it is clear that the weight average numerator obtained by GPC constant is 8700 ~ 293 and the weight average molecular weight obtained by GPC constant.

The weight average molecular weight obtained by mixing with 9 00 4,000 S and GPC is 900 to 24,000, preferably about 3600 to 2400, more preferably 3600 to 00 Yes, there is provided a hydraulic water-reducing method for producing hydraulic water-reduced water containing S, which has 7 to 33 of the total pit product under 4000 molecules obtained by GPC. In this case, high S means that the Pita product under molecule 4 obtained by GPC determination is 2 to 3 in total, and that 3 to 6 is obtained, and S is below 4000 molecules obtained by GPC determination. It is preferable to use a product having a peta product of 33 to 3 8 as a whole, more preferably 34 to 3 8. And S from the viewpoint of improving strength

S is preferably mixed at a solid ratio, that is, by weight, at a low SS 8 20 to 20 80 80 80 to 40 60, more preferably 80 20 to 60 40. Increasing the rate tends to improve the flow. Increasing the ratio tends to reduce the amount of water reducing agent required to achieve the same mobility. Also, S is preferably from 2500 to 3500, more preferably from 2,800 to 3,200, from the viewpoint of improving the weight average molecular weight, flow and strength. Also,

S is preferably from 2000 to 22 from the viewpoint of improving the weight average molecular weight, flow and strength.

In addition, S is usually obtained by condensing formaldehyde of 0 · 60 to 097 to Thalensphone, so that a hydraulic water reduction containing clear S is obtained using this response. You can also. For this reaction, 3-5 to 37 degrees of formalin is used. (Condensation time at that time) By adjusting the ratio of formaldehyde, S which is a weight average molecular pita can be obtained. For example, if the reaction period is lengthened, the weight average molecule tends to increase, and if the reaction period is shortened, the weight average molecule tends to decrease. Also, increasing the formaldehyde ratio tends to increase the weight average molecule, and decreasing the formaldehyde ratio tends to decrease the weight average molecule.

For example, Tarenshon is a formaldehyde of 0 · 6 to 0 · 9 7 and 8 5 to an alkyltalensphone having an alkyl group of prime number ~ 4.

A clear water reduction for hardness can be obtained by a production method having a process of 4 to 5 at 95 C and 4 to 30 at 00 to 0. That is, to the reaction system (which may contain water) containing alkyltalensphonic acid having an alkyl group having a talensphone prime number of -4, formaldehyde at a rate of 85-95, between 4-5, etc. And neutralize the resulting reaction at 0 to 0oC for 4 to 30.

Physically, for Thalens Hong, 0 ・ 60 ～ 0 ・ 9 7 Preferably, 0 · 60 to 0 · 80, more preferably 0 · 60 to 0 · 70 formaldehyde is 85 C.

The condensation reaction product is obtained by heating at 95 C for 4 to 5 and at 0 to 05 C for 4 to 30, preferably 4 to 2, and more preferably 4 to 7. Against the reaction product.

Add 8-0 and let the solution dissolve at a temperature of 50 ° C. to 95 ° C., preferably about 65 ° C. to 85 ° C. over a period of 2 to 2 minutes. (100 to 20) of calcium oxide is added to the dissolved material, and after fractionation as gypsum, neutralized sodium oxide or sodium is added and calcium is used, and then the calcium carbonate is separated. Temperature) from 20 C to 80 C, preferably 20 C. By adjusting from C to 60 C and from 2.0 to 2.5, preferably from 7.0 to 0, it is possible to obtain water reduction for hardness in the form of an aqueous solution containing a sodium salt of S. Water-reduced hydraulic water reduction

30 43 preferably 40 to 43. It can also be obtained by removing moisture. Talence Hong Holm Al Hyd compound

Alkaline, ammonium and amine are preferred. Sodium salt is preferred in the sense of al-salt.

0 · 9 5 to · 02 are preferred. In the light, it is not necessary to add a low-final anhydrous polymer, which is an effective retarding dispersant for slump loss,

It provides reduced water containing S with a distribution. By using a clear water-reducing water, it becomes easy to control the slope according to the nature of the hydraulic property. For example, it is about 30 after hydraulic Appropriate slump loss can be imparted according to the performance of the application, such as applications where the product is desired to be about 60 after hydraulic production (con). When the average molecular weight and pita are satisfied in a clear range, the flow rate increases as the number of compounds under 400 in S increases, and the flow decreases as the number of compounds under 400 million decreases. In consideration of this, slump loss according to the application can be given. The weight average molecular weight S, for example, the average molecular weight S of less than 900, contains many compounds under the molecule 4, but is poor in flow. Thus, when S is simply used in combination with S having a weight average molecular weight of 8,000 to 000 degrees that has been used in the industry, it is expected that the flow cannot be expected. However, in the meantime, in the average molecular S within a predetermined range, the effect of increasing the flow and the strength can be obtained by setting the pita specific rate below 4,000 molecules. This is an exceptional result that cannot be measured from the conventional viewpoint. It is preferable from the viewpoint of fluidity and strength that the pita product under the molecule 400 0 obtained by C constant is 1 7 3 8 in the case of clear water reduction for lightness. 33 to 38 is more preferable, 3 4 to 3 6 is more preferable, and when S is mixed, 24 to 3 3 is preferable, and 2 7 to 3 3 is more preferable.

In the case of light water use for hardness and aqueous solution, it is preferable to have S according to the present invention of 30 to 42 35 to 42, and further 39 to 42. Also, in the case of,, it may consist of S according to the present invention. Light hardened water, other public cement), for example, performance AE, fluidizing agent, AE), AE, delay, early, accelerator, quenching, water retention, crack, high molecular weight, water soluble molecule, blast furnace Sura, fly assy, silica fume, expansion, gradual dispersant, gradual use are possible. In addition, when combined with water reduction, water reduction selected from lignin type hon) (lamin melamine hon formaldehyde compound) is preferred.

It is used to reduce the water used for lightness, and to make the S related to light become 0 ・ 3 ～ 3 ・ 0, more than 0 ・ 5 ～ 3 ・ 0, and more ・・ 0 ～ 3.0 It is preferable.

The hydraulic substance used for the hydraulic property that is the object of light is a substance that reacts with water to form, and one substance does not have curability, but when two or more are combined, water is Cement and gypsum are preferred as substances that form hydration through mutual use. Ordinary portland cement, light cement, medium cement, cement, cement, cement, etc., and blast furnace slurry, fly ash, silica hum, stone powder (Lucium), etc. may be added to these. In addition, as these materials, the hydraulic properties finally obtained by adding sand and gravel are generally called mortar and contour, respectively. For the field of self-leveling, for the leveling, for the leveling, for the leveling, for the plaster, for the plaster slurry, for the light weight, for the A, for the repair, for the pre-patter, for the tremi, for the claut, for the ground, for the cold. Is also useful. Hydraulic and hard substance to become a bright object Slurry of water and hydraulic substance in slurry (Normally written as WP, but written as W when hydraulic substance is cement. 2 5 to 55, 3 more 5 ~ 5 5, \ 4 ~, and further 40 ~ 0. Similar to the water reduction for clear hardness and conventional water reduction containing S, it is considered to be hydraulic such as cement plague, mortar, and contour. Usually, the water of the hydraulic substance is from the start of water to the time after water injection or until it is mixed, and it is not limited. And a hydraulic method having a step of mixing water by any method of B) to 3). Among these, 3) is preferable from the viewpoint of reducing effect. Also, methods ~ 3) may be performed in combination. Method Water start to hard substance Add at the same time

Method 2) Add to hard water

Method 3 Add after the hard substance is finished and before mixing.

Also, high SS related to the water reduction for lightness may be added separately to the hydraulic material. When added to the above, the desired hydraulic fluidity and fluidity can be adjusted. For this addition, it is only necessary that the weight average molecular weight obtained by GPC determination and the pixel product under nnn satisfy the clear range when blended with the above. Further, it may be mixed with a clear water reducing agent and added to the hard substance. Describe the implementation of It is intended to describe the clarification, not to limit the clarification.

Combined ingredients

Of Talence Hong S)

Tallen is charged, and 9 8 · 2 8 is poured into 20 C. Next, the target tarensphonic acid is obtained by changing the temperature to 60 C. 340.

2 S

2 S)

Talence Hong 2 and 2

Place it in the container 90.

Add 3-7 formalin (formal form between 0 and 70 4 to C. Then add 8 to 0 corresponding to 2 to 4 from 5 to dissolve the gel and stop the reaction. That is, the weight average molecular pixel S

0 3) is obtained. After the separation of the compound with liming solderium lucium as the acid, the sodium is separated with sodium carbonate and the lucium is separated, and the solidity is adjusted to 40 to obtain S of It was.

2 2) 2 S)

Put Thalensphone 2 and 2 in the container and put 90 ° C and 0 · 977) as 4 7 From 5 to 0, from 30 to 3 Add 8 ~ 0 to dissolve the gel and stop the reaction to obtain S (~ 13) which is a weight-average molecular weight. Neutralize the compound in the same way as synthesis and adjust the solidity to 40 And gained various S's.

The ratio of the average numerator of S obtained in 2 and the pit below the 4,000 molecule obtained by GPC determination to the pita is shown.

Other decrease

Demon R Co., Ltd. 2 890, Pic 3 5)

2 shares) A 50 a) Uniform molecules 4 5 0 0, pita 7)

3 A Co., Ltd. 200 Co., Ltd. S Co., Ltd. Of rain polymer, S9 9

. The average molecule of 500, Pita 7)

4 (Supernatant after strain 200 W was added. (The average molecular weight of 4500, 7)

2 No-contour test

Using the above-mentioned composite components, the water reduction for hardness shown in 2 and 3 was prepared, and the slump value with respect to the contartite changes with time.

The degree was evaluated. The results are shown in Tables 2 and 3. This was done after the concrete movement due to the following contact condition and after the air.

Made of contact

A predetermined amount of water was added to a 60-degree biaxial mixer corresponding to the amount of contact cement 0, and after 20 hours, a predetermined amount of water reduced as shown in 2 and 3 was added to 70.

Contamination condition

Cement Portland Cement Peiyo Cement Co., Ltd. Cement Co.) 3 6 3) 40 0

Michimizu 70

(2 5 5 3) 94

Degree 2 ・ 7 2 3) 8 5

2. Adjusted by reducing the water so that the initial slump value of contour was 20 0 0. Contalite volume is 5103 by adding Formetta 797 (manufactured by Nikka Corporation) 5 Adjusted in the same way. The concrete was 20.

Contamination dynamics

In accordance with the JSA 0 method, the slump was determined over time. That is, the slump was determined over time for the contours immediately after completion, after 30 minutes, after 60, and after 90. A 0 8 and (2) was determined over time 2

Claims

The weight average numerator obtained by (1) (1) and the mass average molecular weight of 900 to 24,000 obtained by the GPC method, and the pita product below the 4000 molecule obtained by the GPC method is

Water reduction for hydraulic use, containing tarens phone formaldehyde compound that is 7 to 3 8.

, R is a hydrogen atom alkyl of ˜4, is a condensation, and the number is an ion. The hydrogen atom of general 1). 2

The weight average numerator obtained from the Lupa Etion Taro Ruffy GPC is from 8 7000 to 2 9 300

Talence phon formaldehyde compound, called high S), and having the structure of 1) above. Weight average molecular weight of 900 to 400 000 obtained by gel permeation chromatography GP C

Talence Hong Formaldehyde compound, low S) A water-reducing water for use as claimed. Three

S and S combined S

S) is 80 2 0 to 20 8 0

The peak product under the molecule 4 nn obtained by S and GPC is 2 to 7 for all the pixels, and the peak product under the molecule 4,000 obtained by the constant is 3 R to 3 R g for all the pixels. There is a water reduction for stiffening according to claim 2 or 3. Five

Tarenshon Prime Numbers of formaldehyde 0 · 6∼0 · 7 8 5-9 5 to alkyl tarenshon with alkyl groups of ~ 4. The water-reducing water for use as claimed in claim, comprising a step of neutralizing a step of 4 to n between 0 and 10 between 4 and 5 in C. 6

The weight average numerator obtained by GLP analysis with Lupa Etion Tarotography 8 7 0-2 9 300

Talence Hong Formaldehyde compound and the above) Luminescence water reduction according to any one of claims 1 to 4, which comprises a step of mixing with a weight-average molecular weight of 900 to 400 000, which is obtained by constant permeation chromatography (PC). 7

(4) A hydraulic material having a water-reducing water content, a hydraulic material, and water according to any one of the following methods (4) to (3).

Add the hard material to the water start at the same time

Method 2) Add to hard water

Method 3) Add to the mixture after the hard substance.