TWI784130B - Additives for hydraulic compositions - Google Patents

Abstract

The present invention provides an additive for a hydraulic composition comprising a first component including higher fatty acids including unsaturated fatty acids and saturated fatty acids, and a second component including organic amines. In addition, it may further have a third component, and the third component includes at least one fatty alcohol phosphate.

Description

Additives for hydraulic compositions

The invention relates to an additive for a hydraulic composition. In detail, it relates to a high air retention rate, which can improve the stability of its own aqueous solution, has excellent compatibility with known additives for hydraulic compositions, and can improve the concrete obtained from hydraulic compositions. Freeze-thaw resistance additive for hydraulic compositions such as hardened bodies.

In recent years, hardened bodies obtained from hydraulic compositions, such as concrete hardened bodies, have been increasingly required to have high durability. It is known that "freeze-thaw resistance" is one of the indicators showing the high durability of hardened concrete. Therefore, for the purpose of improving the freeze-thaw resistance of hardened concrete, AE concrete in which fine air cells are mixed inside hardened concrete has been manufactured. However, depending on various conditions such as various materials used in hardened concrete or the mixing ratio of various materials, even AE concrete may not have sufficient freeze-thaw resistance. Therefore, various adjustments such as increasing the amount of air or modifying the recipe are performed according to the manufacturing conditions.

For example, in the process of making AE concrete, additives are used to adjust the amount of air. At this time, the freeze-thaw resistance of the obtained hardened concrete varies depending on the type of additives used. Here, there are documents that propose the use of an AE modifier using a phosphate-based additive as an additive excellent in freeze-thaw resistance (refer to Patent Documents 1 and 2).

[Prior Art Literature]

patent documents

Patent Document 1: Japanese Invention Publication No. 2010-100478

Patent Document 2: Japanese Invention Publication No. 2010-285291

However, the phosphate-based additives shown in the above-mentioned Patent Documents 1 and 2 still have a problem of lack of compatibility between water and known additives for hydraulic compositions in terms of application, so that they can only be used limitedly to the above-mentioned additives. method. In addition, when the above-mentioned additives are used, the air retention rate in the concrete may be insufficient due to the material conditions of the concrete, etc. In addition, the processing properties of the concrete may decrease over time, and the workability of the concrete during laying may also decrease. Case.

Therefore, in view of the above facts, there is provided a high air retention rate, good stability itself and excellent compatibility with known additives for hydraulic compositions, and the resulting hardened concrete can show good resistance. Freeze-thaw additives for hydraulic compositions are the main subject of the additives for hydraulic compositions of the present invention.

In order to solve the above-mentioned problems, the inventors of the present case, as a result of intensive research, found an additive for a hydraulic composition containing a specific higher fatty acid and a specific organic amine, or a hydraulic composition that further includes a fatty alcohol phosphate in the above composition. Additives for food are particularly preferred.

That is, the present invention relates to an additive for a hydraulic composition composed of the following components: the first component comprising a higher fatty acid comprising unsaturated fatty acid and saturated fatty acid represented by the following chemical formula 1; and comprising the following chemical formula 2 The second component of the organic amine shown.

Chemical formula 1 R ¹ COOM ¹

However, in the above chemical formula 1, R ¹ COO represents a residue obtained by removing the hydrogen in the carboxyl group from a fatty acid having 10 to 24 carbons, and M ¹ represents hydrogen, an alkali metal or an alkaline earth metal.

In Chemical Formula 1, R ¹ COO is a residue obtained by removing hydrogen in the carboxyl group from a fatty acid having 10 to 24 carbon atoms, and M ¹ represents hydrogen, an alkali metal, and an alkaline earth metal. As related R ¹ COO, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, octadecanoic acid, isostearic acid, octadecenoic acid, Trans-11-octadecenoic acid, linolenic acid, sublinolenic acid, oleostearic acid, eicosic acid, meadic acid, eicosatetraenoic acid, behenic acid, erucic acid, lignoceric acid, etc. A residue obtained by removing hydrogen from a carboxyl group in a fatty acid having 10 to 24 carbon atoms.

In Chemical Formula 1, R ¹ COO is a residue obtained by removing the hydrogen in the carboxyl group from a fatty acid with 10 to 24 carbon atoms, but R ¹ COO is preferably a residue obtained by removing the hydrogen in the carboxyl group from a fatty acid with 12 to 20 carbon atoms.

In addition, the ratio of unsaturated fatty acid and saturated fatty acid in the first component is not particularly limited, but preferably 50 to 99% by mass of unsaturated fatty acid, 1 to 50% by mass of saturated fatty acid, more preferably 70 to 99% by mass of unsaturated fatty acid %, saturated fatty acid 1~30% by mass

100的條件。 However, in the above chemical formula ² , R2 represents an alkyl group having 1 to 30 carbons or an alkenyl group having 2 to 30 carbons, AO and BO represent an oxyalkylene group having 2 to 4 carbons, respectively, and a and b are 0 or more An integer that satisfies a+b

100 conditions.

In Chemical Formula 2, R ² is an alkyl group having 1 to 30 carbons or an alkenyl group having 2 to 30 carbons. Examples of R include methyl, ethyl, ^propyl , butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Eicosyl, Docosyl, Thirty-two Alkyl, tetradecyl, octadecenyl or octadecadienyl, etc. R2 may be a group obtained by removing an amino group from an amine such as tallow amine, ^hydrogenated tallow amine, coconut amine, palm amine or soy amine.

R ² may consist of a linear or branched structure. R ² has a carbon number of 1 to 30, and most preferably 6 to 22. When the carbon number of R2 is greater ^than 30, this organic amine can increase hydrophobicity.

In Chemical Formula 2, AO and BO are oxyalkylene groups having 2 to 4 carbon atoms, preferably oxyethylene groups or oxypropylene groups, more preferably oxyethylene groups. a and b represent the addition moles of oxyalkylene groups.

100的整數。a、b優選為滿足1

a+b

50的整數，更優選為滿足2

a+b

50的整數，特別優選是滿足2

a+b

35的整數，最優選為滿足3

a+b

35的整數。 In Chemical Formula 2, a and b are integers greater than or equal to 0, and satisfy a+b

An integer of 100. a, b preferably satisfy 1

a+b

An integer of 50, more preferably satisfying 2

a+b

An integer of 50, particularly preferably satisfying 2

a+b

An integer of 35, most preferably satisfying 3

a+b

An integer of 35.

In addition, the present invention may further contain a third component containing at least one aliphatic alcohol phosphate ester shown in Chemical Formulas 3, 4, and 5 below, respectively.

chemical formula 4

However, in the above chemical formulas 3 to 5, R ³ to R ⁷ represent residues obtained by removing hydroxyl groups from aliphatic alcohols having 6 to 24 carbon atoms, or residues obtained by removing hydroxyl groups from aliphatic alcohols having 6 to 24 carbon atoms per mol. Alcohol is the residue obtained by removing hydroxyl groups from the product obtained by adding ethylene oxide and/or propylene oxide in a total amount of 1 to 10 moles. N represents an integer of 2 or 3, M2 to M5 represent hydrogen atoms, alkali metals or alkaline earth metals, 1 to 10 moles of propylene oxide are added in total, and at least one of M2 to M5 contains alkali metals or alkaline earth metals.

Examples of R ³ include (1) obtained from hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propyl-heptanol, undecyl alcohol, dodecyl alcohol, Alcohol, 2-Butyloctanol, Tridecyl Alcohol, Myristyl Alcohol, Cetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl Alcohol, Eicosanol, Docosanol, Myristyl Alcohol The residue obtained by removing the hydroxyl group from an aliphatic alcohol having 6 to 24 carbon atoms, or (2) by removing the hydroxyl group from every 1 mole of hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, Decyl Alcohol, 2-Propyl-Heptyl Alcohol, Undecyl Alcohol, Dodecyl Alcohol, 2-Butyl Octyl Alcohol, Tridecyl Alcohol, Myristyl Alcohol, Cetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl alcohol, eicosanol, docosanol, tetracosanol and other aliphatic alcohols with carbon numbers of 6 to 24 are added with a total of 1 to 10 moles of ethylene oxide and/or propylene oxide. The residue obtained by removing the hydroxyl group from the obtained product, etc. Wherein, ^R is preferably selected from octanol, 2-ethylhexanol, nonanol, dodecanol, 2-butyl octanol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, iso A residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 22 carbon atoms such as stearyl alcohol, oleyl alcohol, eicosanol, and docosanol.

Examples of the aliphatic alcohol phosphate represented by Chemical Formula 3 include monohexyl phosphate, monooctyl phosphate, mono-2-ethyl-hexyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl Phosphate, Monobutyl Octyl Phosphate, Monotetradecyl Phosphate, Monomyristate Phosphate, Monooctyl Phosphate, Monostearyl Phosphate, Monoisostearyl Phosphate, Monooleyl Phosphate Ester, monoeicosyl phosphate, monophosphate phosphate, monotetradecyl monophosphate, etc.

In Chemical Formula 4, R ⁴ and R ⁵ are the same as R ³ described in Chemical Formula 3. Therefore, its detailed description is omitted.

The aliphatic alcohol phosphate represented by Chemical Formula 4 can be exemplified by triisooctyl phosphate, dioctyl phosphate, di-2-ethylhexyl phosphate, dinonyl phosphate, didecyl phosphate, dodecyl Phosphate, di-2-butyloctyl phosphate, tridecyl phosphate, dimyristyl phosphate, hexadecyl phosphate, distearyl phosphate, diisostearyl phosphate, di Oleyl phosphate, didecyl oleyl phosphate, sebasyl phosphate, behenyl phosphate, tetracosyl phosphate, etc.

In Chemical Formula 5, R ⁶ and R ⁷ are the same as R ³ described in Chemical Formula 3. Therefore, its detailed description is omitted. In addition, n is an integer of 2 or 3.

The aliphatic alcohol phosphate represented by Chemical Formula 5 can be exemplified by monohexyl pyrophosphate, dihexyl pyrophosphate, monooctyl pyrophosphate, dioctyl pyrophosphate, mono-2-ethylhexyl pyrophosphate, di- 2-Ethyl-hexyl pyrophosphate, monononyl pyrophosphate, dinonyl pyrophosphate, monododecyl pyrophosphate, behenyl pyrophosphate, monooleyl pyrophosphate, di Oleyl pyrophosphate, lauryl oleyl pyrophosphate, dioleyl polyphosphate, etc.

In addition, the higher fatty acid of the first component may also be a residue in which R ¹ COO in the above chemical formula 1 is obtained by removing hydrogen in the carboxyl group from a fatty acid with 12 to 20 carbons.

In addition, the organic amine of the second component may also be an alkyl group or an alkenyl group having 6 to 22 carbon atoms in the above chemical formula ² .

Also, the total acid value of the higher fatty acid of the first component and the fatty alcohol phosphate of the third component is not particularly limited, but may be, for example, within a range of 0.1 mg/g to 500 mg/g. Preferably it is in the range of 10 mg/g to 400 mg/g, more preferably in the range of 50 mg/g to 250 mg/g, most preferably in the range of 100 mg/g to 250 mg/g.

Here, the acid value is, for example, a value calculated as follows. The method is to mix a mixture of isopropanol and xylene/isopropanol (volume ratio 1/1) or a sample dissolved in a solvent such as water with 0.1N potassium hydroxide ethylene glycol/isopropanol (volume ratio 1/1). ) mixed solution, using a potentiometric automatic titration device to carry out potentiometric automatic titration, and using the following formula 1 to calculate the mg number of potassium hydroxide required to neutralize the acidic groups of higher fatty acids and phosphate esters contained in 1g of the sample and obtain value.

Formula 1 acid value (KOH mg/g)=(A1×f1×5.61)/W1

The symbols in the above formula 1 represent respectively:

A1: Titration (ml)

f1: titer of 0.1N potassium hydroxide solution

W1: Sample amount (g)

In addition, the amine value of the organic amine of the second component is not particularly limited, but may be in the range of 20 mg/g to 200 mg/g. Preferably it is in the range of 30 mg/g to 150 mg/g, most preferably in the range of 30 mg/g to 100 mg/g.

The amine value is, for example, the value calculated in the following manner, using isopropanol, a mixed solution of xylene/isopropanol (volume ratio 1/1), or a sample dissolved in a solvent such as water and 0.1N ethylene glycol hydrochloric acid For the mixed solution of salt/isopropanol (volume ratio 1/1), use the potentiometric automatic titration device to perform potentiometric titration, and measure the end point titration (ml), and then use the following formula 2 to calculate and neutralize the organic amine contained in 1g of the sample The value calculated from the mg of potassium hydroxide equivalent to hydrochloric acid required for the amino group.

Formula 2 Amine value (KOH mg/g)=(A2×f2×5.61)/W2

The symbols in the above formula 2 represent respectively:

A2: Titration (ml)

f2: titer of 0.1N hydrochloric acid solution

W2: Sample amount (g)

Furthermore, the numerical value X (%) obtained by the following equation is in the range of 10 to 300.

[The amine value of the second component × the mass of the second component)/{(the total acid value of the acid value of the first component plus the acid value of the third component)×(the mass of the first component plus the mass of the third component The total quality of}]×100,

Here, the above-mentioned numerical value X (%) is preferably 30-250, more preferably 40-200, and most preferably 50-150.

The organic amine salt of fatty alcohol phosphate constituting the additive for the hydraulic composition of the present invention is obtained by the following method: aliphatic alcohol with 6 to 24 carbons or aliphatic alcohol with 6 to 24 carbons per mol A product obtained by adding ethylene oxide and/or propylene oxide to an alcohol in a total ratio of 1 to 10 moles, reacting, for example, phosphorus pentoxide to obtain a fatty alcohol phosphate, and then using the fatty alcohol phosphate as It is obtained by neutralizing alkaline components such as potassium hydroxide and an organic amine shown in Chemical Formula 2. The aforementioned fatty alcohol phosphate is usually a mixture of the fatty alcohol phosphate shown in Chemical Formula 3 and the fatty alcohol phosphate shown in Chemical Formula 4, but it may be a mixture containing the fatty alcohol phosphate shown in Chemical Formula 5 according to circumstances.

The additive for hydraulic compositions of the present invention is used in hydraulic compositions containing hydraulic binders such as civil engineering, construction or secondary products. Examples of the hydraulic composition include paste, mortar, concrete and the like.

The additive for hydraulic compositions of the present invention can be used in combination with existing additives for hydraulic compositions. Examples of the additive for the hydraulic composition include AE water reducer, high performance AE water reducer, AE agent as an air volume modifier, defoamer, shrinkage reducer, thickener, curing accelerator and the like.

As the hydraulic binder used to prepare the hydraulic composition used as the additive for the hydraulic composition of the present invention, in addition to various Portland cements such as ordinary Portland cement, early-strength Portland cement, and medium-heat cement, Various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement can also be exemplified. Various mixed materials such as blast furnace slag fine powder, fly ash, silica fume, etc. can also be used in combination with the above-mentioned various cements.

In addition, when aggregates are used to prepare hydraulic compositions, examples of aggregates include fine aggregates and coarse aggregates, and examples of fine aggregates include river sand, mountain sand, sea sand, crushed sand, slag fine aggregates Wait. Examples of coarse aggregate include river gravel, crushed stone, lightweight aggregate, and the like.

In addition, the water-binder ratio of the hydraulic composition is usually 70% or less, preferably 20% to 60%, more preferably 30% to 55%, particularly preferably 35% to 55%. Generally speaking, when the water-binder ratio increases, the freeze-thaw resistance of the hydraulic composition will decrease, and when the current ratio exceeds 70%, the desired freeze-thaw resistance often cannot be obtained.

The achievable effect of the additive for hydraulic composition of the present invention is that in addition to having a higher air retention rate, the stability of its own aqueous solution is high, and the solubility (miscibility) between known additives for hydraulic composition is high. , As a result, the hardened body obtained has excellent freeze-thaw resistance.

Hereinafter, in order to make the structure and effect of this invention more concrete, each Example is enumerated, but this invention is not limited to these Examples. In the following examples and comparative examples, unless otherwise specified, "part" means parts by mass, and "%" means % by mass.

1. Example 1 (AE-1) (preparation of aqueous solution of additive for hydraulic composition)

810.5 parts of ion-exchanged water, 42.5 parts of oleic acid, and 7.5 parts of stearic acid were added to the reaction vessel, and 3.1 parts of 48% potassium hydroxide aqueous solution was added dropwise while stirring to neutralize. A part of the obtained mixture was sampled, and the water contained in the mixture was dried, and the acid value was measured by potentiometric titration, and the result was 172 mg/g. 136.4 parts of dodecyl-polyoxyethylene 20 molar adduct (amine value 55 mg/g) was added dropwise therein for neutralization to prepare an aqueous solution of an additive for a hydraulic composition (Example 1 (AE-1) ).

2. Examples 2-11 ((AE-2)-(AE-11)), Example 20 (AE-20), Example 27 (AE-27) and Example 28 (AE-28).

Examples 2 to 11 ((AE-2) to (AE-11)), Example 20 (AE-20), and Example 27 in which aqueous solutions of additives for hydraulic compositions were prepared in the same manner as in Example 1 above were prepared. (AE-27) and Example 28 (AE-28). They are prepared in such a way that the amount of Chemical Formula 1 is 5% by mass when M ¹ is hydrogen in an aqueous solution of additives for hydraulic compositions.

3. Example 12 (AE-12)

Add 25.6 parts of 1-octanol to the reaction vessel, and carry out dehydration treatment at 120°C and 0.05MPa for two hours. Phosphorus was added over 0.5 hours. After aging at 80° C. for 3 hours, 0.8 parts of ion-exchanged water was added and aged for 0.5 hours. After adding 10.6 parts of oleic acid and 1.9 parts of stearic acid to this, 13.6 parts of 48% potassium hydroxide aqueous solution was dripped and neutralized at 50 degreeC. A part of the obtained mixture was sampled, and the water contained in the mixture was dried, and the acid value was measured by potentiometric titration to be 221 mg/g. 119.1 parts of dodecyl-polyoxyethylene 20 molar adduct (amine value 55 mg/g) was added dropwise at 50°C to neutralize it, and ion-exchanged water was added to make the hydraulic composition an additive. In the aqueous solution, when M ¹ ~ M ⁵ are all hydrogen, the amount of Chemical Formula 1 and Chemical Formula 3 ~ Chemical Formula 5 becomes 5% by mass, and the aqueous solution of the additive for the hydraulic composition is prepared (Example 12 (AE-12)).

4. Examples 13 to 19 ((AE-13) to (AE-19)), Examples 21 to 26 ((AE-21) to (AE-26)), Examples 29 to 31 ((AE-29 )~(AE-31)) and Comparative Example 2 (RAE-2)

In the same manner as above-mentioned Example 12, Examples 13 to 19 ((AE-13) to (AE-19) ), Examples 21 to 26 ((AE-21) to (AE-26)), Examples 29-31 ((Example 29)-(Example 31)) and Comparative Example 2 (RAE-2). The method of preparation is such that in the aqueous solution of additives for hydraulic compositions, when M ¹ to M ⁵ are all hydrogen, the amount of Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5 becomes 5% by mass.

5. Comparative example 1 (RAE-1)

Add 929.2 parts of ion-exchanged water, 42.5 parts of oleic acid and 7.5 parts of stearic acid into the reaction vessel, and dropwise add 20.8 parts of 48% potassium hydroxide aqueous solution to neutralize while stirring, and prepare the hydraulic composition An aqueous solution of the additive ((Comparative Example 1 (RAE-1)) was used. A part of the resulting mixture was sampled, and after drying the water contained in the mixture, the acid value was measured by potentiometric titration to be 0 mg/g.

6. Comparative example 3 (RAE-3)

Add 25.6 parts of 1-octanol into the reaction vessel, dehydrate at 120°C and 0.05MPa for two hours, return to atmospheric pressure, and add 11.1 parts of 1-octanol dropwise at 60±5°C for 0.5 hours while stirring. Phosphorus pentoxide. After aging at 80° C. for 3 hours, add 0.8 parts of ion-exchanged water and age for 0.5 hours. After adding 10.6 parts of oleic acid and 1.9 parts of stearic acid to this, 34.1 parts of 48% potassium hydroxide aqueous solutions were dripped and neutralized at 50 degreeC. A part of the obtained mixture was sampled, and the water contained in the mixture was dried, and the acid value was measured by potentiometric titration to be 0 mg/g. Add ion-exchanged water to it, so that in the aqueous solution of the additive for the hydraulic composition, when M ¹ ~ M ⁵ are all hydrogen, the amount of Chemical formula 1 and Chemical formula 3 ~ Chemical formula 5 becomes 5% by mass, and the hydraulic composition is prepared. An aqueous solution of the additive was used (Comparative Example 3 (RAE-3)).

7. Comparative example 4 (RAE-4)

The comparative example 4 (RAE-4) of the aqueous solution of the additive for hydraulic compositions was prepared similarly to the said comparative example 1. In this preparation method, in the aqueous solution of the additive for hydraulic compositions, when M ¹ is hydrogen, the amount of the chemical formula 1 becomes 5% by mass.

8. Comparative example 5 (RAE-5)

Add 34.1 parts of 1-octanol into the reaction vessel, dehydrate at 120°C and 0.05MPa for two hours, return to atmospheric pressure, and add 14.8 parts of pentoxide at 60±5°C for 0.5 hours while stirring diphosphorus. After aging at 80° C. for 3 hours, 1.0 parts of ion-exchanged water was added and aged for 0.5 hours. 38.5 parts of a 48% potassium hydroxide aqueous solution was added dropwise thereto at 50° C. for neutralization. A part of the obtained mixture was sampled, and the water contained in the mixture was dried, and the acid value was measured by potentiometric titration to be 0 mg/g. Ion-exchanged water was added thereto so that in the aqueous solution of the additive for the hydraulic composition, when M2 to M5 were all hydrogen, the amount of the chemical formula 3 to the chemical formula 5 became 5% by mass, and the aqueous solution of the additive for the hydraulic composition (compared to Example 5 (RAE-5)).

9. Comparative example 6

932.8 parts of ion-exchanged water and 17.2 parts of 48% potassium hydroxide aqueous solution were charged into the reaction vessel, and then heated to 90°C. Thereto was added 50.0 parts of rosin (manufactured by Wako Pure Chemical Industries, Ltd.) while stirring. After the addition, aging was carried out for 1 hour to prepare an aqueous solution of rosin potassium salt (rosin K).

The contents of the additives for the hydraulic compositions of the examples and comparative examples prepared in 1. to 9. above are comprehensively shown in Table 1 below. The P nuclear integral ratio (P nuclear integration ratio) is calculated in the following manner: For the hydraulic composition additives shown in Table 1 that contain fatty alcohol phosphate as the third component, excess KOH is added to make the pH value The measured values when supplied to ³¹ P-NMR (MERCURY plus NMR Spectrometer System, 300 MHz, trade name manufactured by VALIAN Co., Ltd.) under the condition of 12 or more were calculated from the following formulas 3 to 5. As a solvent, a mixed solution of heavy water/tetrahydrofuran=8/2 (volume ratio) was used.

*1) C: carbon number , F: number of unsaturated bonds , E: addition mole number of oxyethylene

*2) X= [Amine value of the second component × mass of the second component) / {(acid value of the first component plus the acid value of the third component, the total acid value) × (mass of the first component plus The total mass of the mass of the third component}]×100

Here, in the above-mentioned formula 3 to formula 5, "P chemical formula 3 represents: the P core NMR integral value attributed to the organic amine salt of the fatty alcohol phosphate represented by chemical formula 3", "P chemical formula 4 represents: P nuclear NMR integral value attributed to the organic amine salt of the fatty alcohol phosphate represented by chemical formula 4" and "P chemical formula 5 means: attributed to the organic amine salt of the fatty alcohol phosphate represented by chemical formula 5 and other P-nuclear NMR integral values".

In addition, in the above-mentioned Table 1, "Chemical formula 3 represents: P core integral ratio calculated by self-calculation formula 3", "Chemical formula 4 represents: P core integral ratio calculated by self-calculation formula 4" and "Chemical formula 5 represents: self-calculation formula 5 The calculated P core integral ratio".

In addition, in the first component (unsaturated fatty acid), C16F1 represents palmitoleic acid, C18F1 represents oleic acid (only C18F2 of AE-10 represents linoleic acid, only C18F3 of AE-11 represents: linolenic acid), and C22F1 Indicates erucic acid, and in the first component (saturated fatty acid), C10 represents capric acid, C12 represents lauric acid, C14 represents myristic acid, C16 represents palmitic acid, and C18 represents stearic acid (only AE-7 iso- C18 represents isostearic acid. In the third component (fatty alcohol phosphate) R3-R7 respectively represents from C8: octanol, C9: nonanol, C12: lauryl alcohol, and C18F1: oleyl alcohol (only, only AE- C18F1E4 of 21 and AE-25 represent oleyl alcohol-polyoxyethylene 4 molar adducts) residues in which the hydrogen in the carboxyl group is removed. In R2 of the ^second component (organic amine), C8 represents octyl, and C12 represents lauryl base, and C18 represents a stearyl group, and others, K represents a potassium salt, Na represents a sodium salt, and EO represents oxyethylene. Here, the above is a simplified representation of the structure of the first component, the second component and the third component, followed by The number following C indicates "carbon number", and the number following F indicates "number of unsaturated bonds". Furthermore, E indicates oxyethylene, and the number following E indicates the added mole number of "oxyethylene" .

10. Synthesis of polycarboxylic acid type water reducer

Add 368.3g of poly(average added moles: 53mol) ethylene glycol mono(3-methyl-3-butenyl) ether to 244.3g of ion-exchanged water to prepare in a reaction vessel, and replace the atmosphere gas with nitrogen, Heat gradually while stirring. The temperature of the reaction system was kept at 70° C. in a warm water bath, and 23.5 g of a 3.5% hydrogen peroxide aqueous solution was added dropwise over 3 hours, while an aqueous solution of 23.5 g of acrylic acid dissolved in 117.5 g of ion-exchanged water was dropped over 3 hours. At the same time, an aqueous solution obtained by dissolving 1.9 g of L-ascorbic acid and 1.9 g of 3-mercaptopropionic acid in 15.0 g of ion-exchanged water was dripped over 4 hours and allowed to react. 45.5 g of 30% aqueous sodium hydroxide solution and ion-exchanged water were added to the obtained copolymer to obtain a 40% aqueous solution of a water-soluble vinyl copolymer (water reducer B solution). As a result of analyzing this water-soluble vinyl copolymer, the mass average molecular weight was 45,000. The mass average molecular weight of the copolymer is measured by gel permeation chromatography.

11. Measurement conditions

Device: Shodex GPC-101 (manufactured by Showa Denko)

Column: OHpak SB-G+SB-806 M HQ+SB-806 M HQ (manufactured by Showa Denko)

Detector: Differential Refractometer (RI)

Eluent: 50mM sodium nitrate aqueous solution

Flow rate: 0.7mL/min

Column temperature: 40°C

Sample concentration: eluate solution with a sample concentration of 0.5% by mass

Standard substance: PEG/PEO (manufactured by Agilent)

12. Stability of aqueous solution of additives for hydraulic compositions and compatibility with water reducing agents (known additives for hydraulic compositions)

12-1. Stability of aqueous solution of additive for hydraulic composition

The aqueous solution of the additive for the hydraulic composition prepared in Table 1 was shaken and mixed sufficiently, put into a transparent container, and left to stand at 5°C, 20°C, and 40°C for 1 week, and the solubility was checked visually, and the following Evaluation benchmark evaluation. The results are summarized in Table 2 below.

12-2. Compatibility of aqueous solution of additives for hydraulic composition and water reducer

TUPOL is an AE composite agent for polycarboxylic acid type high-performance AE superplasticizer TUPOL HP-11 (manufactured by Takemoto Oil & Fat Co., Ltd - superplasticizer A solution), superplasticizer B solution, modified lignosulfonic acid and polycarboxylic acid compounds EX60 (manufactured by Takemoto Oil & Fat Co., Ltd - superplasticizer C solution), naphthalene superplasticizer (Mighty 150 (manufactured by Kao - superplasticizer D solution)), and acrylate 100 (manufactured by Nissan Chemical Industry Co., Ltd. - superplasticizer E) Solution), add the additive for the hydraulic composition so that the aqueous solution of the additive for the hydraulic composition becomes 1% by mass, and leave the mixture at 20° C. for 1 week, and confirm the solubility visually, and evaluate the standard described below Evaluation. The results are summarized in Table 2 below.

12-3. Evaluation criteria for stability and compatibility

A: Dissolve for more than 1 week

B: Dissolved for more than 1 day, but separated within 1 week

C: Separation within 1 day

13. Preparation and Evaluation of AE Concrete Composition

13-1. Preparation of AE concrete composition

Under the formula condition described in table 3, in the 50L disc type strong kneading mixer, drop into the ordinary Portland cement of fixed amount respectively (the ordinary Portland cement that Pacific Ocean cement manufactures, Ube Mitsubishi cement manufactures, Sumitomo Osaka cement manufactures) Equal mixture, density=3.16g/cm ³ ), land sand (produced in the Oigawa River system, density=2.58g/cm ³ ), gravel (crushed stone produced in Okazaki, density=2.66g/cm ³ ), superplasticizer A solution Or water reducer B solution, aqueous solution of additives for hydraulic compositions, and 0.0005% of the concrete mass defoamer AFK-2 (manufactured by Takemoto Oil Co., Ltd.) and kneading water (tap water) are dropped into and kneaded for 90 seconds, An AE concrete composition with an assumed slump of 18 ± 1 cm and an assumed air volume of 4.5 ± 0.5% was prepared, and the freeze-thaw durability index was obtained. The durability index (300 cycles) in the freeze-thaw test was obtained as the slump, The index of air volume and freeze-thaw resistance (please refer to the detailed description below), the results are summarized in Table 4. In addition, in the case of using the water reducer C solution, the same test was performed under the formulation conditions shown in Table 5. The results are summarized in Table 6.

13-2. Measurement of air volume, slump and durability index in freeze-thaw test

Air content (volume %): The AE concrete composition immediately after kneading was measured in accordance with JIS A 1128.

Slump (cm): Measured simultaneously with the measurement of the air volume in accordance with JIS A 1101.

Durability index in freeze-thaw test: The durability index was obtained according to JIS A 1148 for the cured body of the AE concrete composition prepared using the aqueous solution of the additive for hydraulic composition of each Example. The maximum value of this value is 100, and the closer to 100, the better the freeze-thaw resistance is.

Here, in Table 4 and Table 6, the usage-amount of the water reducing agent and the usage-amount of the aqueous solution of the additive for hydraulic compositions represent the mass percentage with respect to concrete (C).

13-3. Evaluation criteria for freeze-thaw resistance

The degree of freeze-thaw resistance was evaluated based on the following evaluation criteria. That is, the durability index in the freeze-thaw test is 80% or more as A, and the durability index as lower than 80% is B.

From the results shown in Table 2, Table 4 and Table 6, it can be seen that the additive for hydraulic compositions of the present invention has a high air retention rate, and its own stability is excellent, and it is comparable to conventional hydraulic compositions. The solubility (compatibility) between the additives was good, and as a result, it was confirmed that the resulting hardened concrete and the like were excellent in freeze-thaw resistance.

Claims (7)

An additive for a hydraulic composition, used in a hydraulic composition containing a hydraulic binder, the additive for the hydraulic composition is composed of the following components: the first component includes the following chemical formula 1 Higher fatty acids containing unsaturated fatty acids and saturated fatty acids; and the second component, including organic amines shown in the following chemical formula 2; chemical formula 1 R ¹ COOM ¹

Wherein, R ¹ COO represents the residue that removes the hydrogen in the carboxyl group from the fatty acid of carbon number 10-24, M ¹ represents hydrogen, alkali metal or alkaline earth metal; And, wherein R ² represents the alkyl group of carbon number 1 to 30 or Alkenyl groups with 2 to 30 carbons, AO and BO respectively represent oxyalkylene groups with 2 to 4 carbons, a and b represent integers of 0 or more, and satisfy a+b

The condition of 100, wherein the unsaturated fatty acid of the first component is 50-99% by mass, and the saturated fatty acid is 1-50% by mass, wherein the hydraulic binder does not contain fly ash cement. The additive for a hydraulic composition according to claim 1, wherein the unsaturated fatty acid of the first component is 70 to 99% by mass, and the saturated fatty acid is 1 to 30% by mass. The additive for hydraulic composition as described in Claim 1, and further contains a third component, the third component at least contains at least More than one fatty alcohol phosphate;

Among them, R ³ to R ⁷ represent the following residues: residues obtained by removing hydroxyl groups from aliphatic alcohols with carbon numbers of 6 to 24; The residue obtained by removing the hydroxyl group from the product of adding ethylene oxide and/or propylene oxide in a ratio of 1 to 10 moles, n represents an integer of 2 or 3, and ^M2 to ^M5 represent hydrogen, alkali metal or an alkaline earth metal, and at least one of ^M2 to ^M5 contains an alkali metal or an alkaline earth metal. The additive for a hydraulic composition as described in claim 1, wherein the higher fatty acid of the first component is a residue obtained by removing hydrogen in the carboxyl group from a fatty acid having 12 to 20 carbon atoms in the above chemical formula ¹ . As the additive for the hydraulic composition as described in claim 1, wherein the organic amine of the aforementioned second component is R in the above chemical formula 2 ² is an alkyl or alkenyl group with 6 to 22 carbon atoms. The additive for hydraulic compositions as described in claim 3, wherein the total acid value of the acid value of the first component and the acid value of the third component is in the range of 0.1 to 500 mg/g, and the amine of the second component is The valency is in the range of 20 to 200 mg/g. The hydraulic composition additive as described in claim 6, wherein the numerical value obtained by the following equation is in the range of 10 to 300, [(the amine value of the aforementioned second component×the quality of the aforementioned second component)/{( The total acid value of the acid value of the first component plus the acid value of the third component)×(the total mass of the mass of the first component plus the mass of the third component}]×100.