Lignin derivative and additive for hydraulic composition containing same

Abstract

[Problem] To provide a lignin derivative that can be produced by industrially reasonable reaction conditions and can exhibit stable high fluidity by enhancing material uniformity in the initial stage of kneading of a hydraulic composition, and to provide an additive for a hydraulic composition containing the lignin derivative. [Solution] Provided is a lignin derivative which is a reaction product of a mixture containing a lignosulfonic acid-based compound, an aromatic compound, and an aldehyde compound, wherein the lignin derivative has a (poly)alkyleneoxy group with a phosphate-esterified terminal.

Description

Lignin derivative and additive for hydraulic composition containing same

[0001] The present invention relates to a lignin derivative and an additive for a hydraulic composition containing the same.

[0002] Lignin is a natural polymer compound found in trees, and lignin sulfonate, which is contained in sulfite pulp waste liquor discharged from the papermaking process, has long been used as a dispersant for cement, dyes, etc. In recent years, it has attracted attention as a renewable wood-derived biomass material, and further utilization is being considered.

[0003] For example, Patent Document 1 discloses a dispersant containing a lignin derivative formed from a reaction product of a lignin sulfonate salt and a water-soluble monomer having a polyalkylene oxide chain. Patent Document 2 discloses a dispersant containing a lignin derivative compound that is a reaction product of a lignin sulfonate compound and a water-soluble aromatic compound, and Patent Document 3 discloses a dispersant containing a lignin derivative that satisfies predetermined conditions such as viscosity and surface tension.

[0004] Japanese Patent Application Laid-Open No. 2011-240224 International Publication No. 2019 / 039609 Pamphlet Japanese Patent Application Laid-Open No. 2020-025935

[0005] However, depending on the type of lignin sulfonate available as a raw material and the ratio of lignin purity, the reaction may not proceed sufficiently under industrially reasonable reaction conditions, or the reaction may become uncontrollable, resulting in gelation. Therefore, it is difficult to say that conventional lignin derivatives have achieved satisfactory performance as dispersants. In particular, when a lignin derivative is used as a dispersant for a hydraulic composition, there is a problem that the mixed material lacks uniformity during the mixing process of cement, mortar, or concrete, resulting in the fluidity of the hydraulic composition not satisfying the desired performance. In light of the recent trend toward energy conservation and decarbonization, the use of biomass raw materials is being considered, and this lack of uniformity during the mixing process is a major issue that can lead to a decrease in the productivity of hydraulic compositions. Therefore, a higher level of uniformity of the mixed material is required, leaving room for improvement.

[0006] The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a lignin derivative and an additive for hydraulic compositions containing the same, which can be produced under industrially reasonable reaction conditions and can exhibit stable high fluidity by improving the material uniformity of the hydraulic composition at the initial stage of mixing.

[0007] As a result of extensive research, the present inventors have found that a specific lignin derivative having a (poly)alkyleneoxy group at the end of which is phosphate esterified can improve the material uniformity of a hydraulic composition in the initial stage of mixing, thereby enabling the hydraulic composition to exhibit stable high fluidity, and have completed the present invention.

[0008] That is, the present invention is directed to the following [1] to [6]. [1] A lignin derivative which is a reaction product of a mixture containing a lignosulfonic acid compound, an aromatic compound (excluding the lignosulfonic acid compound), and an aldehyde compound, the lignin derivative having a (poly)alkyleneoxy group whose terminal is phosphate esterified. [2] The lignin derivative according to [1], wherein the aromatic compound contains compound A represented by the following formula (1): (wherein n represents 1 or 2, and when n represents 1, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; １ O represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents A １ the average number of moles of O added is 1 to 300, and X １ represents a phosphate group, and when n represents 2, R １ is -CH ２ -, -C(CH ３ ) ２ - or -SO ２ represents -, A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents A １ the average number of moles of O added is 1 to 300, and X １represents a phosphate ester group.) [3] The lignin derivative according to [2], wherein the content of the compound A relative to the total mass of the aromatic compound is 3 mass% or more. [4] The lignin derivative according to [2], wherein the aromatic compound further contains a compound B represented by formula (2): (wherein q represents 1 or 2, and when q represents 1, R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms; p represents A ２ R represents the average number of moles of O added, which is a number from 1 to 300; ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms; when q represents 2, R ３ is -CH ２ -, -C(CH ３ ) ２ - or -SO ２ represents -, A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms; p represents A ２ R represents the average number of moles of O added, which is a number from 1 to 300; ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.) [5] The lignin derivative according to [1], wherein the aldehyde compound is compound C represented by formula (3): (In the formula, R ４ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group, and r represents a number from 1 to 100. [6] The lignin derivative according to [1], which is a reaction product of a mixture containing the lignin sulfonic acid compound and the aromatic compound in a mass ratio of lignin sulfonic acid compound:aromatic compound = 20:80 to 35:65. [7] An additive for hydraulic compositions, containing the lignin derivative according to any one of [1] to [6].

[0009] The lignin derivative of the present invention can be produced under industrially reasonable reaction conditions, and when added as an additive to a hydraulic composition, it can improve the uniformity of the material at the initial stage of mixing, thereby enabling the hydraulic composition to exhibit stable high fluidity.

[0010] The lignin derivative of the present invention and the additive for hydraulic compositions containing the same will be described in detail below.

[0011] <Lignin Derivative> The lignin derivative of the present invention is a reaction product of a mixture containing a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and has a (poly)alkyleneoxy group with a terminal phosphate ester. The "terminally phosphated (poly)alkyleneoxy group" refers to a structure in which a phosphate ester group is introduced at one end of a (poly)alkyleneoxy group. Examples of phosphate esters constituting the phosphate ester group include phosphate monoesters and salts thereof, phosphate diesters and salts thereof, phosphate triesters, and mixtures thereof. Among these, from the viewpoint of imparting high fluidity to hydraulic compositions, it is preferable to contain a phosphate ester group composed of a phosphate monoester represented by the following formula and a salt thereof: *-O-P(=O)(-OM) ２ (M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as calcium or magnesium; an ammonium group; or an organic ammonium group such as an alkylammonium group or an alkanolammonium group. * represents a bond to another group (structure).)

[0012] The (poly)alkyleneoxy group is composed of repeating units (alkyleneoxy units) derived from alkylene oxide. The number of carbon atoms in the alkyleneoxy unit is not particularly limited, but is typically 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the alkylene oxide (alkyleneoxy unit) include ethylene oxide (ethyleneoxy unit), propylene oxide (propyleneoxy unit), and butylene oxide (butyleneoxy unit), with ethylene oxide and propylene oxide being preferred. These alkylene oxides can be used alone or in combination of two or more. When two or more alkylene oxides are used to form a (poly)alkyleneoxy group, the alkylene oxides may be added in either random or block form. The average number of moles of alkylene oxide units added is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less. In a (poly)alkyleneoxy group having a phosphated terminal, the terminal of the (poly)alkyleneoxy group that is not phosphated may be bonded directly or via a linking group to a structural unit derived from a lignin sulfonic acid compound of a lignin derivative, or may be bonded similarly to a structural unit derived from an aromatic compound, or may be bonded to both, but is preferably bonded to a structural unit derived from an aromatic compound.

[0013] <Lignosulfonic Acid Compound> In the present invention, the lignosulfonic acid compound refers to a compound having a skeleton in which a carbon atom at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group. The compound may also be one that has been chemically modified by hydrolysis, alkoxylation, desulfonation, alkylation, or the like.

[0014] The lignosulfonic acid compound may be in the form of a salt, such as a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic ammonium salt, of which calcium salt, magnesium salt, or sodium salt is preferred.

[0015] The production method and origin of the lignosulfonic acid compound are not particularly limited, and either natural or synthetic products may be used. Lignin sulfonic acid compounds are one of the main components of sulfite pulp waste liquor obtained by cooking wood under acidic conditions. Therefore, lignosulfonic acid compounds derived from sulfite pulp waste liquor may be used. Commercially available lignosulfonic acid compounds may also be used. Examples of commercially available products include sodium lignosulfonate manufactured by Tokyo Chemical Industry Co., Ltd., Vanilex (registered trademark) HW, Vanilex N, etc. (manufactured by Nippon Paper Industries Co., Ltd.), Sanex (registered trademark) M, Sanex P321, Sanex P252, Sanex SCL, Sanex SCP, etc. (manufactured by Nippon Paper Industries Co., Ltd.), Pearllex (registered trademark) NP, Sanex DP, etc. (manufactured by Nippon Paper Industries Co., Ltd.), Sunflow (registered trademark) RH (manufactured by Nippon Paper Industries Co., Ltd.), and Greensperse S9 (manufactured by Borregaard).

[0016] <Aromatic Compound> In the present invention, the aromatic compound refers to a compound having at least one aromatic skeleton, other than the lignosulfonic acid compound, which undergoes a condensation reaction with a lignosulfonic acid compound to form a copolymer. Examples of the aromatic compound include a phenolic compound having a (poly)alkyleneoxy group phosphated at the end (compound A represented by formula (1) described below), an alkylene oxide adduct of a phenolic compound or a derivative thereof (compound B represented by formula (2)), as well as phenols and non-phenolic aromatic compounds having no phenolic hydroxy group.

[0017] <Compound A represented by formula (1) (aromatic compound A)> Compound A is a phosphate derivative of an alkylene oxide adduct of a phenolic compound such as phenol or bisphenol A, and has a structure represented by the following formula (1): The aromatic compound of the present invention preferably contains at least compound A represented by formula (1). In the above formula, n represents 1 or 2, and R １ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms when n is 1, and represents -CH ２ -, -C(CH ３ ) ２- or -SO ２ - represents. １ O represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents A １ the average number of moles of O added is 1 to 300; X １ represents a phosphate ester group.

[0018] The compound A is a phosphate derivative of a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a substituted phenolic compound such as phenol or bisphenol A. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added singly or in combination, and when two or more alkylene oxides are used, they may be added in either a block or random manner.

[0019] That is, the above A １ Examples of the alkyleneoxy group having 2 to 4 carbon atoms represented by O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. １ O may be composed of only an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or may contain two or more of these groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition. Furthermore, m is A １ The average number of moles of O added is 1 to 300, preferably 2 to 200, and more preferably 3 to 150.

[0020] When n is 1, the above R １Examples of the hydrocarbon group having 1 to 24 carbon atoms include an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group having 4 to 24 carbon atoms and two or more unsaturated bonds, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 24 carbon atoms. Examples of the alkyl group having 1 to 24 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (palmityl), octadecyl (stearyl), icosyl, docosyl (behenyl), and tetracosyl groups, which may have a branched structure (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc.) and / or a cyclic structure (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, etc.). Examples of the alkenyl group having 2 to 24 carbon atoms include the same alkyl groups having 2 to 24 carbon atoms as those mentioned above for the alkyl group, but having one carbon-carbon double bond. Specific examples include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl, eicosenyl, docosenyl, and tetracosenyl groups, which may have a branched structure and / or a cyclic structure.Furthermore, examples of the unsaturated aliphatic hydrocarbon group having 4 to 24 carbon atoms and two or more unsaturated bonds include a decadienyl group, an undecadienyl group, a dodecadienyl group, a tridecadienyl group, a tetradecadienyl group, a pentadecadienyl group, a hexadecadienyl group, a heptadecadienyl group, an octadecadienyl group, a nonadecadienyl group, an icosadienyl group, a henicosadienyl group, a docosadienyl group, a tricosadienyl group, Examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those described above. Specific examples of the aralkyl group having 7 to 24 carbon atoms include, but are not limited to, a phenylmethyl group (benzyl group), an α-methylbenzyl group, a 2-phenylethyl group, a 1-methyl-1-phenylethyl group (cumyl group), a 3-phenyl-propyl group, and a 2-phenyl-2-propyl group.

[0021] When n is 2, the above R １ Ha-CH ２ -, -C(CH ３ ) ２ - or -SO ２ In addition, in both cases where n is 1 and where n is 2, R in formula (1) represents １ The bonding position of is not particularly limited, but it is preferable that it is bonded to the para position relative to the oxygen atom bonded to the aromatic ring, in order to easily exert the effects of the present invention. For example, when n is 1, R １ is preferably a hydrogen atom or a tert-butyl group, and when n is 2, R １ is -C(CH ３) ２ It is preferable that −.

[0022] Compound A is a phosphoric acid monoester and / or its salt, a phosphoric acid diester and / or its salt, a phosphoric acid triester, or a mixture thereof. Examples of the phosphoric acid ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium. Compound A may be synthesized by a known method using a phosphorylating agent on a (poly)oxyalkylene alkylphenol. Examples of the phosphorylating agent include phosphoric anhydride, phosphoric acid, polyphosphoric acid, and phosphorus oxychloride.

[0023] As the compound A represented by the above formula (1), for example, when n is 1, the compound A can be a compound represented by the following formula: １ , A １ O and n are the same as defined in the above formula (1), and Ph represents a phenylene group. M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as calcium or magnesium; an ammonium group; or an organic ammonium group such as an alkylammonium group or an alkanolammonium group. Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R"-O-(A'O)w- (wherein R" represents an alkyl group having 1 to 24 carbon atoms, A'O represents an alkyleneoxy group having 2 to 3 carbon atoms, i.e., an ethyleneoxy group or a propyleneoxy group, and w represents the average number of moles of alkyleneoxy groups A'O added, which is 1 to 300). When a plurality of Z's are present, they may be the same or different groups. - Phosphoric acid monoesters and salts thereof R １ -Ph-O-[A １ O] ｍ -P(=O)(-OM) ２ Phosphate diesters and their salts [R １ -Ph-O-[A １ O] ｍ -] ２P(=O)(-OM) [R １ -Ph-O-[A １ O] ｍ −](Z−)P(═O)(−OM) phosphate triester [R １ -Ph-O-[A １ O] ｍ -] ３ P(=O) [R １ -Ph-O-[A １ O] ｍ -] ２ (Z-)P(=O) [R １ -Ph-O-[A １ O] ｍ −] (Z−) ２ P(=O)

[0024] The compound A represented by the formula (1) can be used alone or in combination of two or more. From the viewpoint of obtaining stable high fluidity, the content ratio of compound A to the total mass of aromatic compounds is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, and the aromatic compounds may be composed only of compound A (100 mass%). When the content ratio of compound A in the aromatic compounds is 10 mass% or more, it can be expected that the uniformity of the kneaded material will be improved.

[0025] <Compound B Represented by Formula (2) (Aromatic Compound B)> In addition to compound A represented by formula (1) above, the aromatic compound may further include compound B having a structure represented by formula (2) below. In the above formula, q represents 1 or 2, and R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms when q is 1, and represents -CH ２ -, -C(CH ３ ) ２ - or -SO ２ - represents. ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms; p represents A ２ R represents the average number of moles of O added, which is a number from 1 to 300; ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

[0026] The compound B is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a phenolic compound such as phenol or bisphenol A, or a substituted product thereof, and derivatives of the alkylene oxide adduct (alkyl esters or fatty acid esters) are also encompassed in compound B. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added singly or in combination, and when two or more alkylene oxides are used, they may be added in either a block or random manner.

[0027] That is, the above A ２ Examples of the alkyleneoxy group having 2 to 4 carbon atoms represented by O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. ２ O may consist solely of ethyleneoxy, propyleneoxy, or butyleneoxy groups, or may contain two or more of these groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.

[0028] p is the average number of moles of alkyleneoxy groups added, and represents a number of 1 to 300, preferably 10 to 200, and more preferably 20 to 150; A ２ By increasing the number of moles of O added, improvement in water reducing property can be expected.

[0029] The above R ２ The alkyl group having 1 to 10 carbon atoms in the formula (I) may have a branched structure and / or a cyclic structure. １Among the groups given as specific examples of the alkyl group having 1 to 24 carbon atoms in the above, alkyl groups having 1 to 10 carbon atoms can be mentioned. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, and a 1-adamantyl group. Examples of the acyl group having 2 to 24 carbon atoms include saturated or unsaturated acyl groups (R'(CO)- group, where R' is a hydrocarbon group having 1 to 23 carbon atoms). Examples of saturated acyl groups having 2 to 24 carbon atoms include carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecylic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), and tetracosanoic acid (lignoceric acid); Examples of the acyl groups derived from fatty acids include monounsaturated acyl groups derived from monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; diunsaturated acyl groups derived from diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; and triunsaturated acyl groups derived from triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, and eicosatrienoic acid.

[0030] When q is 1, the above R ３ Specific examples of the hydrocarbon group having 1 to 24 carbon atoms in R １ When q is 2, the same as R ３ Ha-CH ２ -, -C(CH ３ ) ２ - or -SO ２In addition, when q is 1 and when q is 2, R in formula (2) represents -. ３ The bonding position of is not particularly limited, but it is preferable that it is bonded to the para position relative to the oxygen atom bonded to the aromatic ring, in order to easily exert the effects of the present invention. For example, when q is 1, R ３ is preferably a hydrogen atom or a tert-butyl group, and when q is 2, R ３ is -C(CH ３ ) ２ It is preferable that −.

[0031] The compound B represented by the formula (2) can be used alone or in combination of two or more. The content of the compound B in the aromatic compound is not particularly limited, but can be the remainder excluding the compound A.

[0032] <Other Aromatic Compounds> In the lignin derivative of the present invention, the aromatic compound may contain, in addition to the above-mentioned Compound A and Compound B, other aromatic compounds capable of reacting with these compounds, as long as the effects of the present invention are not impaired. Examples of other aromatic compounds include phenol, bisphenol A, isophthalic acid, oxynaphthoic acid, benzoic acid, hydroxybenzoic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, anilinesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and hydroxyethylphenol.

[0033] <Aldehyde Compound> As the aldehyde compound, a compound C having a structure represented by the following formula (3) can be preferably used. In the formula, R ４represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group, and r represents a number from 1 to 100. These alkyl groups, alkenyl groups, phenyl groups, naphthyl groups and heterocyclic groups may be substituted with any substituent, such as an alkyl group having 1 to 10 carbon atoms; an aryl group such as a phenyl group or a naphthyl group; a halogen atom such as a chlorine atom or a bromine atom; a sulfonic acid functional group such as a sulfo group or a sulfonate group; an acyl group such as an acetyl group; a hydroxy group; an amino group; or a carboxyl group. ４ The alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms in the formula (1) may have a branched structure or a cyclic structure, and specific examples thereof include R １ Among the groups given as specific examples of the alkyl group having 1 to 24 carbon atoms and the alkenyl group having 2 to 24 carbon atoms in the above formula, alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms can be given. Furthermore, examples of the heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a piperidyl group, and a morpholino group. Furthermore, r preferably represents a number of 2 to 100.

[0034] Examples of the compound C (aldehydes) include formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, dodecanal, acrolein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylic aldehyde, and benzyl aldehyde [(C ６ H ５ ) ２C(OH)-CHO), naphthaldehyde, furfural, etc., among which, it may be selected from the group consisting of formaldehyde, paraformaldehyde, benzaldehyde, or any mixture of two or more thereof. Compound C can be used as a pure crystal or powder substance, or as a hydrate thereof, or in the form of an aqueous solution such as formalin, which simplifies the measuring or mixing of the components.

[0035] The compound C represented by the above formula (3) can be used alone or in combination of two or more.

[0036] <Reaction Ratio of Each Compound> In the present invention, the reaction ratio of the lignosulfonic acid compound to the aromatic compound is not particularly limited, but the mass ratio of the lignosulfonic acid compound to the aromatic compound is preferably 1 / 99 to 99 / 1, and from the viewpoint of achieving both a high biomass content and fluidity of the hydraulic composition, it is more preferably 10 / 90 to 90 / 10, even more preferably 20 / 80 to 75 / 25, and particularly preferably 20 / 80 to 55 / 45. Furthermore, for example, a mass ratio of the lignosulfonic acid compound to the aromatic compound of 20 / 80 to 40 / 60 can be expected to achieve more stable and high fluidity, and particularly a mass ratio of 20 / 80 to 35 / 65 can be expected to achieve even more stable and high fluidity. Even if a reaction product of a mixture containing a lignosulfonic acid compound, an aromatic compound, and an aldehyde compound contains unreacted components of the compounds, the mass ratio (reaction ratio) of the total amount of structural units derived from the lignosulfonic acid compound and unreacted lignosulfonic acid compound components to the total amount of structural units derived from the aromatic compound and unreacted aromatic compound components will be the same as the charge ratio. Furthermore, the reaction amount of the aldehyde compound relative to the total amount of the lignosulfonic acid compound and the aromatic compound is not particularly limited, but the mass ratio of the total amount to the aldehyde compound is preferably 99 / 1 to 80 / 20, more preferably 98 / 2 to 85 / 15, for example 98 / 2 to 90 / 10.

[0037] <Lignin Derivative and Production Method Thereof> The lignin derivative of the present invention is a reaction product of a mixture containing the above-mentioned lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and includes a copolymer obtained by polycondensation of the mixture. The ratio (feed ratio) of the lignin sulfonic acid compound, aromatic compound, and aldehyde compound used in the polycondensation is not particularly limited. For example, the mass ratio of the lignin sulfonic acid compound to the aromatic compound in the mixture can be 1:99 to 99:1 (lignin sulfonic acid compound:aromatic compound). From the viewpoint of achieving both a high biomass content and fluidity of the hydraulic composition, the mass ratio can be more preferably 10:90 to 90:10, even more preferably 20:80 to 75:25, for example, 20:80 to 55:45, or even 20:80 to 40:60. From the viewpoint of achieving particularly stable high fluidity, the mass ratio can be 20:80 to 35:65. The ratio of the total amount of the lignosulfonic acid compound and aromatic compound to the aldehyde compound in the mixture is not particularly limited. For example, the mass ratio of the total amount to the aldehyde compound may be 99:1 to 80:20, more preferably 98:2 to 85:15, e.g., 98:2 to 90:10. The polymerization method for obtaining the copolymer is not particularly limited. The order or method of adding the lignosulfonic acid compound, aromatic compound, and aldehyde compound during polycondensation is also not particularly limited. For example, all of the raw material compounds may be added at once before the polycondensation reaction; some of the raw material compounds may be added before the polycondensation reaction and the remainder may then be added dropwise; or some of the raw material compounds may be added before the polycondensation reaction and the remainder may be added after a certain reaction time has elapsed. For example, by mixing an aromatic compound and an aldehyde compound before the pre-polycondensation reaction and then adding a lignin sulfonic acid compound dropwise to this mixture, it is expected that the molecular weight of the resulting copolymer will be easily controlled.

[0038] Lignin derivatives can be obtained, for example, by polycondensing a lignosulfonic acid compound, an aromatic compound, and an aldehyde compound in the presence of a dehydration catalyst, either without a solvent or in the presence of a solvent, at a reaction temperature of 80°C to 150°C under normal pressure to elevated pressure, for example, 0.001 to 1 MPa. Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, dimethyl sulfate, phosphoric acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvic acid, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, and activated clay. These dehydration catalysts may be used alone or in combination of two or more. When polycondensation reactions are carried out in a solvent, the solvent can be water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene and xylene, or cycloaliphatic compounds such as methylcyclohexane. Furthermore, solvents that can be used as dehydration catalysts (acid catalysts), such as acetic acid, can also be used. When polycondensation reactions are carried out in a solvent, the concentrations of the components (lignosulfonic acid compounds, aromatic compounds, and aldehyde compounds) used in the polycondensation reaction in the reaction system can be appropriately selected. However, if the concentration is too high, gelation is likely to occur, and if the concentration is too low, the reaction may not proceed quickly. For example, the components used in the polycondensation reaction can be approximately 30 to 70%. The reaction temperature can be, for example, 95°C to 130°C, and the polycondensation reaction can be completed within approximately 3 to 25 hours. The polycondensation reaction is preferably carried out under acidic conditions, preferably with a pH of 4 or less in the reaction system. An antifoaming agent may be used during the production of the lignin derivative (during the polycondensation reaction), which can suppress foaming during the reaction and create a uniform reaction system.

[0039] After the polycondensation reaction is complete, various known methods can be used to reduce the content of unreacted aldehyde components (compound C) in the reaction system. Examples include: adjusting the pH of the reaction system to an alkaline level and heating the system to 60 to 140°C; reducing the pressure of the reaction system (-0.1 to -0.001 MPa) to volatilize and remove the aldehyde components; and adding small amounts of sodium hydrogen sulfite, hydrogen peroxide, ethyleneurea, and / or polyethyleneimine. The dehydration catalyst used in the reaction can be neutralized after the reaction is complete and removed by filtration in the form of a salt. However, even if the catalyst is not removed, the performance of the additive for hydraulic compositions of the present invention, as described below, is not impaired. In addition to filtration, other methods for removing the catalyst include phase separation, dialysis, ultrafiltration, and the use of an ion exchanger. Neutralizing the reaction product and diluting it with water or the like improves the ease of measurement and other processes when using the additive for hydraulic compositions, as described below. In this case, examples of the basic compound used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, and organic amines such as monoethanolamine, diethanolamine, and triethanolamine, and one or more of these may be used in combination. For example, sodium hydroxide and calcium hydroxide may be used in combination as the basic compound to be subjected to neutralization.

[0040] The weight-average molecular weight Mw of the copolymer finally obtained (measured by gel permeation chromatography (hereinafter referred to as "GPC"), calculated as polyethylene glycol) is preferably in the range of 4,000 to 150,000, more preferably in the range of 8,000 to 120,000, and particularly preferably in the range of 12,000 to 100,000, from the viewpoint of exhibiting excellent dispersibility. The term "lignin derivative" as used herein may refer to a copolymer obtained by polycondensation of a monomer mixture containing a lignosulfonic acid compound, an aromatic compound, and an aldehyde compound, but generally also includes unreacted components and by-products generated in each polymerization step, alkylene oxide addition step, etc.

[0041] <Additives for Hydraulic Compositions> The additive for hydraulic compositions of the present invention contains the lignin derivative. It can also be used in the form of a so-called admixture by appropriately combining known additives for hydraulic compositions according to various applications. Specifically, at least one other additive selected from the group consisting of conventionally known cement dispersants, high-performance air-entraining (AE) water-reducing agents, high-performance water-reducing agents, AE water-reducing agents, air-entraining agents (AE agents), foaming agents, antifoaming agents, set retarders, set accelerators, separation-reducing agents, thickeners, shrinkage-reducing agents, curing agents, and water-repellents can be blended. In the present invention, the hydraulic composition refers to a composition containing a powder (hydraulic powder) that hardens upon hydration, such as cement, gypsum, fly ash, or blast furnace slag. When the hydraulic powder is cement, the hydraulic composition is also referred to as a cement composition.

[0042] Cement dispersants are generally used in appropriate combinations depending on the manufacturing conditions and performance requirements of concrete. The same is true for the additive for hydraulic compositions of the present invention, which can be used alone as a cement dispersant or as a main agent, but can also be used in combination with cement dispersants with high slump loss or with cement dispersants with high initial water reduction. Examples of known cement dispersants include salts of polycarboxylic acid copolymers described in JP-B-59-18338, Japanese Patent No. 2628486, and Japanese Patent No. 2774445, as well as salts of naphthalenesulfonic acid-formalin condensates, salts of melaminesulfonic acid-formalin condensates, lignin sulfonates, sodium gluconate, and sugar alcohols. The blend ratio of the polycondensate of the present invention to the known cement dispersant is, for example, 1:99 to 99:1 by mass.

[0043] Specific examples of air entraining agents include anionic air entraining agents, nonionic air entraining agents, and amphoteric air entraining agents. Examples of setting retarders include inorganic and organic setting retarders. More specific examples include hydroxycarboxylic acids such as gluconic acid, glucoheptonic acid, tartaric acid, citric acid, malic acid, and arabinonic acid, and their salts; sugars such as sucrose; and inorganic compounds such as zinc oxide, zinc chloride, silicofluorides, and silicofluoride salts. Examples of accelerators include inorganic and organic accelerators. Examples of thickeners and separation-reducing agents include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymer thickeners such as diutan gum, welan gum, and xanthan gum, and nonionic thickeners such as polyethylene glycol and polyalkylene oxide. Examples of defoamers include nonionic defoamers, silicone-based defoamers, higher alcohols, and mixtures containing these as main components.

[0044] When the additive for hydraulic compositions of the present invention is applied to, for example, a cement composition, the components constituting the cement composition are conventionally used components for concrete, such as cement (e.g., ordinary Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, low-heat / moderate-heat Portland cement, blast-furnace cement, etc.), aggregate (i.e., fine aggregate and coarse aggregate), admixture (e.g., silica fume, calcium carbonate powder, ground granulated blast-furnace slag, fly ash, etc.), expansive agent, and water.

[0045] The additive for hydraulic compositions of the present invention can also be suitably used in hydraulic compositions (cement compositions) containing fly ash or ground granulated blast furnace slag as admixtures. Fly ash contains silica (SiO ２ ), alumina (Al ２ O ３), and JIS A 6201 specifies standards for types I to IV (JIS A6201) based on particle size and flow value. It is said that there is a correlation between the amount of unburned carbon contained in fly ash and the amount of air entrainment agent used, and that an increase in the amount of unburned carbon tends to lead to an increase in the amount of air entrainment agent used. The amount of unburned carbon is generally said to be correlated with the amount of methylene blue adsorbed by fly ash. Ground granulated blast furnace slag is a by-product of refining iron in a blast furnace, and contains calcium oxide (CaO), silica (SiO ２ ), alumina (Al ２ O ３ ) as its main component, and its standard is specified in JIS A 6206.

[0046] In addition, admixtures other than the additive for hydraulic compositions of the present invention that can be added separately during blending include the above-mentioned publicly known and used air-entraining agents, setting retarders, accelerators, separation-reducing agents, thickeners, antifoaming agents, shrinkage-reducing agents, etc., and these can also be blended appropriately. The blending ratio of each component can be determined appropriately depending on the type of component selected and the purpose of use.

[0047] The amount of the additive for hydraulic compositions of the present invention varies depending on the formulation conditions, including the concrete ingredients, but is typically added in an amount of approximately 0.05 to 5.0 mass% (as the amount of the lignin derivative itself) based on the mass of cement, or, when a pozzolanic fine powder such as fly ash is used, based on the total mass of cement and powder such as fly ash, calculated as solids. The amount added is adjusted appropriately depending on the desired initial flow value, but caution is required as excessive addition can cause delay in setting and, in some cases, poor hardening. The additive for hydraulic compositions of the present invention achieves higher fluidity than conventional products, i.e., it can achieve its performance at a lower addition rate than conventional products. The method of use is similar to that of general cement dispersants: either add the undiluted solution during concrete mixing or dilute it in mixing water before adding it. Alternatively, it can be added after mixing the concrete or mortar and then mixed uniformly again.

[0048] The present invention will be described below with reference to examples, but the present invention is not limited to these examples and comparative examples.

[0049] The weight-average molecular weight of the lignin derivative was measured by the following method: GPC (Gel Permeation Chromatography) <Gel Permeation Chromatography (GPC) Measurement Conditions> Column: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko K.K.) Eluent: Mixture of 50 mM aqueous sodium nitrate solution and acetonitrile (volume ratio 80 / 20) Detector: Differential refractometer, Calibration curve: Polyethylene glycol

[0050] [Production Example 1] (Preparation of aromatic compound A) A glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube was charged with 3 moles of an ethylene oxide (EO) 6 mole adduct of p-tert-butylphenol, and then 1 mole of phosphoric anhydride was charged at 50°C over 4 hours while nitrogen bubbling was performed, and the reaction was allowed to proceed. An aging reaction was then carried out for 3 hours at 100°C to terminate the phosphate esterification reaction, thereby obtaining a phosphate ester (A-1) of an EO adduct of p-tert-butylphenol. Similarly, a phosphate ester (A-2) of an EO 90 mole adduct of p-tert-butylphenol, a phosphate ester (A-3) of an EO 4 mole adduct of bisphenol A, and a phosphate ester (A-4) of an EO 3 mole adduct of p-tert-butylphenol were obtained. (Aromatic Compound B) As aromatic compound B, poly(ethylene oxide) monophenyl ethers having various EO addition mole numbers, an EO 60 mole adduct of bisphenol A, and an EO 44 mole adduct of p-tert-butylphenol were prepared.

[0051] [Example 1] (Production of Lignin Derivative (L-1)) A glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device was charged with 106 g of water, 45 g of poly(ethylene oxide) monophenyl ether (EO addition moles: 90) (aromatic compound B), 3.4 g of the aromatic compound A (A-1) synthesized in Production Example 1, 27 g of sodium lignin sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of 92% paraformaldehyde, 18.1 g of 98% aqueous sulfuric acid solution, and 0.02 g of antifoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.), and the reaction vessel was heated to 105 ° C. over 30 minutes with stirring. After the liquid temperature reached 105 ° C., the reaction was carried out for 7 hours. After completion of the reaction, 42 g of a 250 g / L aqueous calcium hydroxide solution and 7 g of a 48% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for another 1 hour. The mixture was filtered to remove gypsum formed by neutralization, thereby obtaining a liquid product (L-1) of a lignin derivative containing a copolymer having a weight-average molecular weight of 43,200.

[0052] [Example 2] (Production of lignin derivative (L-2)) A glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device was charged with 106 g of water, 2.3 g of the aromatic compound A (A-1) synthesized in Production Example 1, 32.7 g of aromatic compound A (A-2), 38.6 g of sodium lignin sulfonate (Tokyo Chemical Industry Co., Ltd.), 3.8 g of 92% paraformaldehyde, 18.1 g of a 98% aqueous sulfuric acid solution, and 0.02 g of an antifoaming agent Pronal 753W (Toho Chemical Industry Co., Ltd.). The reaction vessel was heated to 105 ° C. over 30 minutes under stirring. After the liquid temperature reached 105 ° C., the reaction was carried out for 7 hours. After completion of the reaction, 42 g of a 250 g / L aqueous calcium hydroxide solution and 7 g of a 48% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for another 1 hour. The mixture was filtered to remove gypsum formed by neutralization, thereby obtaining a liquid product (L-2) of a lignin derivative containing a copolymer having a weight-average molecular weight of 53,000.

[0053] Example 3 (Production of Lignin Derivative (L-3)) A liquid lignin derivative (L-3) containing a copolymer having a weight-average molecular weight of 61,000 was obtained under the same conditions and by the same method as in Example 1, except that 3.4 g of the phosphate ester compound (A-3) synthesized in Production Example 1 was used as the aromatic compound A.

[0054] Examples 4 to 16 (Production of Lignin Derivatives (L-4 to L-10, L-14 to L-19)) Liquid lignin derivatives (L-4) to (L-10) and (L-14) to (L-19) were obtained in the same manner as in Example 1, except that the types of lignin sulfonic acid compound and aromatic compounds (A, B) and the reaction ratios (feed ratios) of each compound were changed as shown in Table 1. When obtaining the liquid lignin derivatives (L-17) and (L18), the lignin sulfonic acid compound was added dropwise.

[0055] [Comparative Example 1] (Production of Lignin Derivative (L-11)) A glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device was charged with 106 g of water, 41.2 g of poly(ethylene oxide) monophenyl ether (EO addition moles: 100), 2.2 g of p-hydroxybenzoic acid, 4.9 g of aniline sulfonic acid, 26.9 g of sodium lignin sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of 92% paraformaldehyde, 18.1 g of 98% aqueous sulfuric acid, and 0.02 g of antifoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.), and the reaction vessel was heated to 105 ° C. over 30 minutes under stirring. After the liquid temperature reached 105 ° C., the reaction was carried out for 7 hours. After completion of the reaction, 42 g of a 250 g / L aqueous calcium hydroxide solution and 7 g of a 48% aqueous sodium hydroxide solution were added to the reaction vessel and stirred for another 1 hour. The mixture was filtered to remove gypsum formed by neutralization, thereby obtaining a liquid product (L-11) of a lignin derivative containing a copolymer having a weight-average molecular weight of 24,000.

[0056] Comparative Example 2 (Production of Lignin Derivative (L-12)) A liquid lignin derivative (L-12) was obtained in the same manner as in Example 1, except that the types of lignin sulfonic acid compound and aromatic compound and the reaction ratio (feed ratio) of each compound were changed as shown in Table 1.

[0057] Comparative Example 3 Commercially available sodium lignosulfonate (L-13) was subjected to the test as it was.

[0058]

[0059] [Fresh mortar test] <Materials and mix>

[0060]

[0061] <Mixing Method> Sand and cement were added to a high-power mixer (manufactured by Maruto Seisakusho Co., Ltd.) in the amounts shown in Table 2, and dry mixing was performed for 10 seconds. Next, water containing lignin derivatives L-1 to L-12, L-14 to L-19 obtained in Examples 1 to 16 and Comparative Examples 1 and 2, or sodium lignin sulfonate (L-3) from Comparative Example 3 (0.25% based on cement) and Pronal 753W (0.01% based on cement) manufactured by Toho Chemical Industry Co., Ltd. was added to the mixer and mixed at low speed for 30 seconds. Once the mixer was stopped, the mixed state of the mortar was visually observed and assigned a rating. 30 seconds after the mixer was stopped, an additional 60 seconds of high-speed mixing was performed to prepare a mortar, which was then subjected to flow measurement. The mixed state of the mortar was evaluated using the following three-point scale, with a rating of ○ or higher being considered good. The results are shown in Table 3. ◎: The materials are mixed evenly, and the mortar surface is very moist. ○: The materials are mixed evenly, and the mortar surface is moist. ×: The materials are not mixed evenly, and the mortar surface is not moist.

[0062] <<Flow Measurement Method>> The spread (flow value) of the test mortar was measured immediately after mixing, and after 30 and 60 minutes using a mini-slump cone (a conical cylinder with an upper inner diameter of 50 mm, a lower inner diameter of 100 mm, and a height of 150 mm) in accordance with JIS A 1171 "Test Methods for Polymer-Cement Mortars." The results are shown in Table 3.

[0063]

[0064] As shown in Table 3, the mortars of Examples 1 to 16 containing the lignin derivative of the present invention exhibited good mixing conditions and maintained high fluidity immediately after mixing, even after 30 minutes and even after 60 minutes. In the technical field of hydraulic compositions such as cement and mortar, a commonly required fluidity requirement is the ability to maintain fluidity for approximately 30 to 60 minutes (retention performance). The results of Examples 1 to 16 fully satisfied the performance requirements in the industry. In particular, Examples 1, 3 to 6, 10, 12 to 14, and 16, in which the lignin sulfonate compound / aromatic compound ratio was 20 / 80 to 40 / 60 (mass ratio), showed little change in fluidity from the initial state even after 60 minutes. In particular, Examples 12 and 16, in which the lignin sulfonate compound / aromatic compound ratio was 20 / 80 to 35 / 65 (mass ratio), showed little difference in flow value after 30 minutes and after 60 minutes, confirming that high fluidity was maintained. Furthermore, it was confirmed that Examples 2, 7 to 9, 12, 13, and 15, in which the proportion of compound A in the aromatic compounds was 10% by mass or more, had excellent material uniformity at the initial stage of mixing.

[0065] Specifically, among Examples 1, 7, and 14, which used the same lignosulfonic acid compound, aromatic compound, and aldehyde compound, Examples 1 and 14, in which the lignosulfonic acid compound / aromatic compound ratio was 20 / 80 to 40 / 60 (mass ratio), were confirmed to maintain high fluidity, although their initial fluidity was somewhat inferior to that of Example 7, which was outside the above range. Furthermore, Example 14, in which the lignosulfonic acid compound was added dropwise, was confirmed to maintain higher fluidity than Example 1, which is thought to be due in part to increased molecular weight uniformity as a polymer due to molecular weight control of the copolymer. Examples 1, 4, and 6, which used the same components and lignosulfonic acid compound / aromatic compound ratios except for the lignosulfonic acid compound, showed no significant difference in material uniformity at the initial stage of mixing, and although there was some variation in initial fluidity, the fluidity after 60 minutes tended to settle to approximately the same value. Similarly, among Examples 8, 15, and 16 in which the three components were the same, it was confirmed that Example 16, in which the lignosulfonic acid compound / aromatic compound ratio was 20 / 80 to 35 / 65 (mass ratio), exhibited excellent initial fluidity and maintained high fluidity compared to Examples 8 and 15, which were outside the above range. It was also confirmed that Example 15, in which the lignosulfonic acid compound was added dropwise, maintained higher fluidity than Example 8. Similarly, among Examples 10 and 12 in which the three components were the same, it was confirmed that Example 12, in which the lignosulfonic acid compound / aromatic compound ratio was 20 / 80 to 35 / 65 (mass ratio), maintained higher fluidity compared to Example 10, which was outside the above range. Comparing Example 7 (number of moles added: 90) and Example 8 (number of moles added: 22), in which the blending amounts of lignosulfonic acid compound / aromatic compound were the same but the number of moles of alkyleneoxy groups added in Compound B was changed, it was confirmed that although the initial fluidity of Example 8 was somewhat inferior to that of Example 7, it tended to maintain high fluidity after 60 minutes had elapsed.

[0066] On the other hand, in the mortars of Comparative Examples 1 to 3, which did not use Compound A as the aromatic compound, the materials were not uniformly mixed, and compared with the Examples, the mortars lacked fluidity immediately after mixing, and lost fluidity after 60 minutes had passed.

Claims

1. A lignin derivative which is a reaction product of a mixture containing a lignin sulfonate compound, an aromatic compound (excluding the above-mentioned lignin sulfonate compound) and an aldehyde compound, and which has a (poly)alkyleneoxy group whose terminal is phosphorylated.

2. The lignin derivative according to claim 1, wherein the aromatic compound comprises compound A represented by the following formula (1): (In the formula, n represents 1 or 2, and when n represents 1, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; １ O represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents A １ The average number of moles of O added is a number from 1 to 300; X １ represents a phosphate group, when n represents 2, R １ is -CH ２ -, -C(CH ３ ) ２ - or -SO ２ - represents A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms; m represents A １ The average number of moles of O added is a number from 1 to 300; X １ represents a phosphate ester group.) 3. The lignin derivative according to claim 2, wherein the content of compound A relative to the total mass of the aromatic compounds is 3 mass% or more.

4. The lignin derivative according to claim 2, wherein the aromatic compound further comprises a compound B represented by formula (2). (In the formula, q represents 1 or 2, and when q represents 1, R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms; p is A ２ R represents the average number of moles of O added, which is a number from 1 to 300; ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms; when q represents 2, R ３ is -CH ２ -, -C(CH ３ ) ２ - or -SO ２ - represents A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms; p is A ２ R represents the average number of moles of O added, which is a number from 1 to 300; ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

5. The lignin derivative according to claim 1, wherein the aldehyde compound is compound C represented by formula (3). (In the formula, R ４ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group, and r represents a number from 1 to 100.

6. The lignin derivative according to claim 1, which is a reaction product of a mixture containing the lignin sulfonic acid compound and the aromatic compound in a mass ratio of lignin sulfonic acid compound:aromatic compound = 20:80 to 35:

65.

7. An additive for hydraulic compositions, comprising the lignin derivative according to any one of claims 1 to 6.