Lignin derivative and additive for hydraulic composition containing same

Abstract

[Problem] To provide: a lignin derivative which can be produced under industrially reasonable reaction conditions, enables a hydraulic composition to stably exhibits high fluidity by enhancing material uniformity of the hydraulic composition, and can therefore impart high material separation resistance thereto; and an additive for a hydraulic composition containing the same. [Solution] A lignin derivative which is a reaction product of a mixture that contains a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and which has a phosphoric acid esterified (poly)alkyleneoxy group at a terminal, wherein the aromatic compound contains a compound X represented by formula (4). (In the formula, Xa represents a group or atom selected from the group consisting of -SH, -CHO, -COOMx, -SO3Mx, -NH2, -CN, -NO2, -P(O)(OMx)2, and a halogen atom, or an organic group containing one or more of these groups and atoms and having 1 to 10 carbon atoms; Mx represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkyl ammonium group, or an alkanol ammonium group; and Xb represents a group or atom selected from the group consisting of a hydrogen atom, -OH, -NH2, -NH(C6H4NH2), and -NH(CO)CH3 (provided that Xa and Xb are not the same group, and when Xb represents a hydrogen atom, Xa represents -P(O)(OH)2).)

Description

Lignin derivatives and additives for hydraulic compositions containing the same

[0001] The present invention relates to lignin derivatives and additives for hydraulic compositions containing the same.

[0002] Lignin is a natural polymer compound found in trees, and lignin sulfonates contained in sulfite pulp wastewater discharged during the papermaking process have long been used as dispersants in cement, dyes, and other materials. In recent years, it has attracted attention as a renewable biomass raw material derived from wood, and further utilization is being considered. For example, Patent Document 1 discloses a dispersant containing a lignin derivative, which is a reaction product of lignin sulfonate and a water-soluble monomer having a polyalkylene oxide chain. Patent Document 2 discloses a dispersant containing a lignin derivative compound, which is a reaction product of a lignin sulfonic acid compound and an aromatic water-soluble compound, and Patent Document 3 discloses a dispersant containing a lignin derivative that satisfies predetermined conditions such as viscosity and surface tension.

[0003] Japanese Patent Publication No. 2011-240224, International Publication No. 2019 / 039609, Japanese Patent Publication No. 2020-025935

[0004] However, depending on the type of lignin sulfonate available as a raw material and the proportion of lignin purity, conventional lignin derivatives may not perform satisfactorily as dispersants. For example, the reaction may not proceed sufficiently under industrially reasonable reaction conditions, or the reaction may not be controllable, resulting in gelation. In particular, when lignin derivatives are used as dispersants for hydraulic compositions, there is a problem that the uniformity of the mixed material after manufacturing cement, mortar, or concrete is insufficient, resulting in the hydraulic composition's resistance to material segregation not meeting the desired performance. In light of the current era of energy conservation and decarbonization, and the consideration of utilizing biomass raw materials, this lack of resistance to material segregation in concrete is a major issue that can lead to a decrease in the durability of structures using hydraulic compositions. A higher level of uniformity of mixed materials is required than before, and there was room for improvement.

[0005] On the other hand, due to concerns about a shortage of high-quality natural aggregates such as river sand and river gravel, and from the perspective of environmental protection, the use of artificial aggregates such as crushed stone and crushed sand in concrete has been increasing in recent years, but this has also given rise to technical problems. Generally, the manufacturing process of crushed stone and crushed sand generates a large amount of crushed stone powder as a byproduct. When crushed stone and crushed sand (i.e., artificial aggregates) containing a large amount of crushed stone powder are used as raw materials for concrete, there is a problem that the amount of water required to obtain the desired slump increases compared to ordinary concrete. Therefore, it is difficult to manufacture high-strength concrete with reduced water content. In addition, during concrete manufacturing, the performance of conventionally known polycarboxylic acid-based water-reducing agents is significantly reduced, and their use becomes excessive, leading to problems such as increased concrete viscosity, poor workability, and significant slump retention loss over time. Furthermore, even with concrete that has ensured fluidity, material segregation may occur during placement on site, and if this is used as is, problems such as cracks and other defects may occur after hardening. Since these technical problems rarely occur when using high-quality land sand and river sand, which are readily available as natural resources, there is a need for technologies that can improve the fresh properties of concrete mixed with crushed stone, crushed sand, and crushed stone powder. In other words, there is growing interest in technologies that resolve the problems that can arise from the use of artificial aggregates, with the aim of achieving both improved concrete quality and reduced environmental impact.

[0006] Furthermore, the aforementioned material segregation and material uniformity are caused by variations in concrete fluidity and density differences between cement paste and aggregate. Therefore, simply selecting concrete materials is insufficient to improve these material segregation and uniformity issues. For these reasons, improving resistance to material segregation and material uniformity has been a desirable feature for dispersants and other materials used in hydraulic compositions, thereby increasing their added value.

[0007] The present invention has been made in view of the above circumstances, and can be produced under industrially reasonable reaction conditions. By enhancing the material uniformity of the hydraulic composition, it can stably exhibit high fluidity, thereby imparting high material separation resistance. Also, even when the type of fine aggregate constituting the hydraulic composition is changed, there are few fluctuations in the addition amount and the manifestation of functions. An object of the present invention is to provide a lignin derivative and an additive for a hydraulic composition containing the same.

[0008] As a result of intensive studies by the present inventors, a predetermined lignin derivative having a (poly)alkyleneoxy group with a phosphorylated terminal and containing a structure derived from a specific aromatic compound can enhance the material uniformity at the initial stage of kneading of the hydraulic composition, and thereby it has been found that a high and stable fluidity can be exhibited with respect to the hydraulic composition, and the present invention has been completed.

[0009] That is, the present invention is directed to the following [1] to [9]. [1] A lignin derivative which is a reaction product of a mixture containing a lignin sulfonic acid compound, an aromatic compound (excluding the lignin sulfonic acid compound) and an aldehyde compound, and which is a lignin derivative having a (poly)alkyleneoxy group with a phosphorylated terminal, wherein the aromatic compound contains a compound X represented by the following formula (4). (In the formula, X ａ represents a group or atom selected from the group consisting of -SH, -CHO, -COOM ｘ , -SO ３ M ｘ , -NH ２ , -CN, -NO ２ , -P(O)(OM ｘ ) ２ and a halogen atom, or represents an organic group having 1 to 10 carbon atoms containing one or more of these groups and atoms, and M ｘ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group or an alkanolammonium group, and X ｂ represents a hydrogen atom, -OH, -NH ２ , -NH(C ６ H ４ NH２ ), and -NH(CO)CH ３ It represents a group or atom selected from the group consisting of (where X ａ and X ｂ They are not the same basis, and X ｂ When X represents a hydrogen atom, ａ ha-P(O)(OH) ２ [2] The lignin derivative according to [1], wherein the compound X is a compound represented by the following formula (4-1). (In the formula, X ａ -SH, -NH ２ , -SO ３ H, -P(O)(OH) ２ , or -CH ２ CHNH ２ Represents COOH, X ｂ represents a hydrogen atom or -OH (however X ｂ When X represents a hydrogen atom, ａ ha-P(O)(OH) ２ [3] The lignin derivative according to [1], wherein the content ratio of compound X to the total mass of the aromatic compound is 1% to 20% by mass. [4] The lignin derivative according to [1], wherein the aromatic compound further comprises compound A represented by the following formula (1). (In the formula, n represents 1 or 2, and when n represents 1, R １ A represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. １ O represents an alkylene oxy group with 2 to 4 carbon atoms, and m represents A １ X represents the average number of moles of O added, ranging from 1 to 300. １ represents a phosphate ester group, and when n represents 2, R １ is, -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ - represents A １ O represents an alkylene oxy group with 2 to 4 carbon atoms, and m represents A １ X represents the average number of moles of O added, ranging from 1 to 300. １(wherein represents a phosphate ester group.) [5] The lignin derivative according to claim 3, wherein the content ratio of compound A to the total mass of the aromatic compound is 3% by mass or more. [6] The lignin derivative according to [1], wherein the aromatic compound further comprises compound B represented by formula (2). (In the formula, q represents 1 or 2, and when q represents 1, R ３ A represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. ２ O represents an alkylene oxy group with 2 to 4 carbon atoms, and p represents A ２ R represents the average number of moles added, ranging from 1 to 300. ２ R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms, and when q represents 2, R ３ is, -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ - represents A ２ O represents an alkylene oxy group with 2 to 4 carbon atoms, and p represents A ２ R represents the average number of moles added, ranging from 1 to 300. ２ (wherein represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.) [7] The lignin derivative according to [1], wherein the aldehyde compound is compound C represented by formula (3). (In the formula, R ４ (wherein 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.) [8] The lignin derivative according to [1], wherein the lignin derivative 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 60:40. [9] An additive for hydraulic compositions containing the lignin derivative according to any one of [1] to [8].

[10] The additive for hydraulic compositions according to [9], which is an additive for hydraulic compositions containing artificial aggregate.

[0010] The lignin derivative of the present invention can be manufactured under industrially rational reaction conditions, and when added as an additive to a hydraulic composition, it can improve the material uniformity of concrete, provide high resistance to material segregation even when stable high fluidity is achieved in the hydraulic composition, and moreover, the amount added and the expression of function can be kept small even when the type of fine aggregate constituting the hydraulic composition is changed.

[0011] The lignin derivatives of the present invention and additives for hydraulic compositions containing them will be described in detail below.

[0012] <Lignin Derivatives> The lignin derivatives targeted by the present invention are reaction products of a mixture containing a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and are lignin derivatives having a (poly)alkylene oxy group with a phosphate ester at one end. "(Poly)alkylene oxy group with a phosphate ester at one end" refers to a structure in which a phosphate ester group is introduced to one end of a (poly)alkylene oxy group. Examples of phosphate esters constituting the phosphate ester group include phosphate monoesters and their salts, phosphate diesters and their salts, phosphate triesters, and mixtures thereof. Among these, from the viewpoint of imparting high fluidity to the hydraulic composition, it is preferable to include a phosphate ester group composed of a phosphate monoester and its salt represented by the following formula: *-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; an organic ammonium group such as an alkylammonium group or an alkanolammonium group. * represents a bond with another group (structure).)

[0013] The (poly)alkylene oxy group is composed of repeating units (alkylene oxy units) derived from alkylene oxide, and the number of carbon atoms in the alkylene oxy unit is not particularly limited, but is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the alkylene oxide (alkylene oxy unit) include ethylene oxide (ethylene oxy unit), propylene oxide (propylene oxy unit), and butylene oxide (butylene oxy unit), with ethylene oxide and propylene oxide being preferred. These alkylene oxides can be used alone or in combination of two or more, and when two or more alkylene oxides are used to construct the (poly)alkylene oxy group, the addition form of these alkylene oxides may be random addition or block addition. 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)alkylene oxy group whose terminal end is phosphorylated, the terminal end of the (poly)alkylene oxy group that is not phosphorylated may be directly or via a linking group bonded to a structural unit derived from a lignin sulfonic acid compound among the lignin derivatives, or similarly bonded to a structural unit derived from an aromatic compound, or bonded to both, but it is preferable that it is bonded to a structural unit derived from an aromatic compound.

[0014] <Lignin Sulfonic Acid Compounds> In the present invention, lignin sulfonic acid compounds refer to compounds having a skeleton in which a sulfo group is introduced by cleaving the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin. Furthermore, the above compounds may be chemically modified by hydrolysis, alkoxylation, desulfonation, alkylation, etc.

[0015] Ligninsulfonic acid compounds can take the form of salts. Examples of salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts, of which calcium salts, magnesium salts, and sodium salts are preferred.

[0016] The method of producing ligninsulfonic acid compounds and their origin are not particularly limited, and they may be either natural or synthetic products. Ligninsulfonic acid compounds are one of the main components of the wastewater of sulfite pulp obtained by pulping wood under acidic conditions. For this reason, ligninsulfonic acid compounds derived from sulfite pulp wastewater may be used. Commercially available ligninsulfonic acid compounds can also be used. Examples of commercially available products include sodium ligninsulfonate manufactured by Tokyo Chemical Industry Co., Ltd., as well as Vanillex® HW, Vanillex® N, etc. (manufactured by Nippon Paper Industries Ltd.), Sunex® M, P321, P252, SCL, SCP, etc. (manufactured by Nippon Paper Industries Ltd.), Pearllex® NP, DP, etc. (manufactured by Nippon Paper Industries Ltd.), Sunflow® RH (manufactured by Nippon Paper Industries Ltd.), and Greensperse S9 (manufactured by Borregard).

[0017] <Aromatic Compounds> In the present invention, an aromatic compound is a compound having at least one aromatic skeleton, which undergoes a condensation reaction with a ligninsulfonic acid compound to produce a copolymer, and is a compound other than the ligninsulfonic acid compound. Examples of aromatic compounds include phenolic compounds having a (poly)alkylene oxy group with a phosphorylated terminal (compound A represented by formula (1) described later), alkylene oxide adducts or derivatives thereof of phenolic compounds (compound B represented by formula (2)), as well as phenols and non-phenolic aromatic compounds that do not have a phenolic hydroxyl group. The present invention is particularly characterized by the use of an aromatic compound (compound X) having a specific structure represented by formula (4) described later.

[0018] <Compound A represented by formula (1) (aromatic compound A)> Compound A is a phosphate ester derivative of an alkylene oxide adduct of a phenolic compound such as phenol or bisphenol A, and has the structure represented by the following formula (1). The aromatic compound of the present invention preferably contains compound A represented by formula (1) in addition to compound X represented by formula (4) described later. In the above formula, n represents 1 or 2, R １When n represents 1, it represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; when n represents 2, it represents -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ Represents -. A １ O represents an alkylene oxy group with 2 to 4 carbon atoms, and m represents A １ The average number of moles of O added, representing a number between 1 and 300, X １ This represents a phosphate ester group.

[0019] Compound A is a phosphate ester derivative of a compound obtained by adding a 2- to 4-carbon alkylene oxide to a phenolic compound such as phenol or bisphenol A, or a substituted thereof. Examples of the 2- to 4-carbon alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added individually or in combination, and when two or more alkylene oxides are used, either block addition or random addition is acceptable.

[0020] That is, A above １ Examples of alkylene oxy groups with 2 to 4 carbon atoms in O include ethylene oxy groups, propylene oxy groups, and butylene oxy groups. １ O may consist only of an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or it may contain two or more of these groups. If it contains two or more groups, the addition form may be random addition or block addition. Also, m is A １ This represents the average number of moles of O added, which is between 1 and 300, preferably between 2 and 200, and more preferably between 3 and 150. When n represents 2, the preferred range of m is 2 or more and 100 or less.

[0021] The above R when n is 1 １Examples of hydrocarbon groups having 1 to 24 carbon atoms include alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, unsaturated aliphatic hydrocarbon groups having 4 to 24 carbon atoms with two or more unsaturated bonds, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 24 carbon atoms. Examples of alkyl groups 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), eicosyl, docosyl (behenyl), and tetracosyl groups, which may have branched structures (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc.) and / or cyclic structures (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, etc.). Examples of alkenyl groups having 2 to 24 carbon atoms include the alkyl groups having 2 to 24 carbon atoms listed above that have one carbon-carbon double bond. Specifically, examples include ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, octadecenyl group, eicocenyl group, dococenyl group, tetracocenyl group, etc., and these may have branched and / or cyclic structures.Furthermore, unsaturated aliphatic hydrocarbon groups having two or more unsaturated bonds between 4 and 24 carbon atoms include decadienyl group, undecadienyl group, dodecadienyl group, tridecadienyl group, tetradecadienyl group, pentadecadienyl group, hexadecadienyl group, heptadecadienyl group, octadecadienyl group, nonadecadienyl group, eicosadienyl group, henicosadienyl group, docosadienyl group, tricosadienyl group, Examples include tetracosadienyl group, decatrienyl group, undecatrienyl group, dodecatrienyl group, tridecatrienyl group, tetradecatrienyl group, pentadecatrienyl group, hexadecatrienyl group, heptadecatrienyl group, octadecatrienyl group, nonadecatrienyl group, eicosatrienyl group, henicosatrienyl group, docosatrienyl group, tricosatrienyl group, and tetracosatrienyl group. Examples of aryl groups having 6 to 20 carbon atoms include phenyl group, naphthyl group, anthryl group, and phenanthryl group, but are not limited to these. Aralkyl groups are alkyl groups substituted with aryl groups, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above. Specific examples of aralkyl groups having 7 to 24 carbon atoms include, but are not limited to, phenylmethyl group (benzyl group), α-methylbenzyl group, 2-phenylethyl group, 1-methyl-1-phenylethyl group (cumyl group), 3-phenylpropyl group, and 2-phenyl-2-propyl group.

[0022] Also, if n is 2, then the above R １ ha-CH ２ -, -C(CH ３ ) ２ -, or -SO ２ This represents -. Note that in both the case where n is 1 and the case where n is 2, R in equation (1) １ The bonding position is not particularly limited, but it is preferable that it is bonded in the para position relative to the oxygen atom bonded to the aromatic ring, as this facilitates the exertion of the effects of the present invention. For example, when n is 1, R １ It is preferable that is a hydrogen atom or a tert-butyl group, and when n is 2, R １ C(CH) ３) ２ - is preferable.

[0023] Compound A is a phosphate monoester and / or a salt thereof, a phosphate diester and / or a salt thereof, a phosphate triester, or a mixture thereof. Examples of the above phosphate ester salts include alkali metal salts such as sodium and potassium; group 2 metal salts such as calcium or magnesium; ammonium salts; and organic ammonium salts such as alkylammonium or alkanolammonium. Compound A may be synthesized by known methods using a phosphorylating agent with (poly)oxyalkylene alkylphenol. Examples of phosphorylating agents include anhydrous phosphoric acid, phosphoric acid, polyphosphate, and phosphorus oxychloride.

[0024] As compound A represented by the above formula (1), for example, when n is 1, compound A can be given as the compound represented by the following formula. In the formula, R １ A １ O and n represent the same elements as defined in formula (1) above, 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; 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 alkylene oxy group having 2 to 3 carbon atoms, i.e., an ethylene oxy group or a propylene oxy group, and w represents the average number of added moles of alkylene oxy group A'O, which is 1 to 300). If there are multiple Zs, they may be the same group or different groups. • Phosphate monoesters and their salts R １ -Ph-O-[A １ O] ｍ -P(=O)(-OM) ２ • Diphosphate esters 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) · Trialkyl phosphate [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)

[0025] The compound A represented by the above formula (1) can be used alone or in combination of two or more. The content ratio of the aromatic compound in compound A is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more from the viewpoint of obtaining stable and high fluidity. For example, the upper limit can be 99% by mass or less, or 98% by mass or less, or 92% by mass or less. When the content ratio of the aromatic compound in compound A is 10% by mass or more, an improvement in the uniformity of the kneaded material can be expected.

[0026] <Compound B (aromatic compound B) represented by formula (2)> As the aromatic compound, in addition to the compound X represented by formula (4) described later and the compound A represented by the above formula (1), a compound B having the structure represented by the following formula (2) may further be included. 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 represents 1, and represents -CH ２ -, -C(CH ３ )( ２ )-, or -SO ２ - when q represents 2. A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, p represents the average addition molar number of A ２ O and represents a number from 1 to 300, and R ２represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

[0027] Compound B is a compound obtained by adding a phenolic compound such as phenol or bisphenol A, or a substituted thereof, to an alkylene oxide having 2 to 4 carbon atoms. Derivatives of the alkylene oxide adduct (alkyl esters or fatty acid esters) are also included 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 individually or in combination, and when two or more alkylene oxides are used, either block addition or random addition is acceptable.

[0028] That is, A above ２ Examples of alkylene oxy groups with 2 to 4 carbon atoms in O include ethylene oxy groups, propylene oxy groups, and butylene oxy groups. ２ O may consist only of an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or it may contain two or more of these groups. If it contains two or more groups, the addition method may be random addition or block addition.

[0029] Furthermore, p represents the average number of added moles of alkylene oxy groups, and is a number from 1 to 300, preferably 10 to 200, and more preferably 20 to 150. ２ By increasing the number of moles of O added, an improvement in water-reducing properties can be expected. When q represents 2, the preferred range for p is 2 or greater and 100 or less.

[0030] The above R ２ The alkyl group having 1 to 10 carbon atoms in the above R may have a branched structure and / or a cyclic structure, specifically the above R １Among the groups listed as specific examples of alkyl groups having 1 to 24 carbon atoms, alkyl groups having 1 to 10 carbon atoms can be cited. Specifically, examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, etc. Examples of acyl groups 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). For example, 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). Fatty acid-derived acyl groups 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, meadic acid, dihomo-γ-linolenic acid, and eicosatrienoic acid.

[0031] The above R when q is 1 ３ Specific examples of hydrocarbon groups having 1 to 24 carbon atoms in R １ The same thing can be cited as above. When q is 2, the above R ３ ha-CH ２ -, -C(CH ３ ) ２ -, or -SO ２This represents -. Note that in both the case where q is 1 and the case where q is 2, R in equation (2) ３ The bonding position is not particularly limited, but it is preferable that it is bonded in the para position relative to the oxygen atom bonded to the aromatic ring, as this allows the effects of the present invention to be easily achieved. For example, when q is 1, R ３ It is preferable that is a hydrogen atom or a tert-butyl group, and when q is 2, R ３ C(CH) ３ ) ２ - is preferable.

[0032] Compound B, represented by formula (2) above, can be used alone or in combination of two or more types. The proportion of compound B in the aromatic compounds is not particularly limited, but it can be the remainder after excluding compound A and compound X described later.

[0033] <Compound X represented by formula (4) (aromatic compound X)> As an aromatic compound, the present invention includes compound X having the structure represented by the following formula (4) as an essential component. In the above formula, X ａ -SH, -CHO, -COOM ｘ , -SO ３ M ｘ , -NH ２ -CN, -NO ２ , -P(O)(OM ｘ ) ２ It represents a group or atom selected from the group consisting of and halogen atoms, or an organic group having 1 to 10 carbon atoms that includes one or more of these groups and atoms. Examples of the organic group include an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms of the alkyl group are substituted with one or more of the above groups and atoms (provided that the organic group as a whole has 1 to 10 carbon atoms). If there are multiple substitutions, the substituted groups and atoms may be the same or different. Also M ｘ X 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, an alkylammonium group, or an alkanolammonium group. ｂThese are hydrogen atoms, -OH, -NH ２ ,-NH(C ６ H ４ NH ２ ), and -NH(CO)CH ３ It represents a group or atom selected from the group consisting of X. ａ and X ｂ They are not the same base, and X ｂ When X represents a hydrogen atom, ａ ha-P(O)(OH) ２ It represents.

[0034] For example, one example of the compound X is the compound represented by the following formula (4-1). In the above formula (4-1), X ａ -SH, -NH ２ , -SO ３ H, -P(O)(OH) ２ , or -CH ２ CHNH ２ Represents COOH, X ｂ represents a hydrogen atom or -OH. However, X ｂ When X represents a hydrogen atom, ａ ha-P(O)(OH) ２ This represents...

[0035] Preferred specific examples of compound X include, but are not limited to, p-hydroxybenzenethiol, p-phenolsulfonic acid, sodium p-phenolsulfonate, p-aminophenol, tyrosine ((S)-4-hydroxy-α-aminobenzenepropanoic acid), phenylphosphonic acid, 4-nitrophenol, 5-amino-2-[(p-aminophenyl)amino]benzenesulfonic acid, 4-acetamidobenzenesulfonamide, p-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, anilinesulfonic acid, p-chlorophenol, p-bromophenol, p-iodophenol, p-fluorophenol, 4-cyanophenol, 4-aminomethylphenol, and 2-(4-hydroxyphenyl)propionic acid.

[0036] The compound X represented by formula (4) above can be used alone or in combination of two or more types. From the viewpoint of obtaining high fluidity and resistance to material separation, the content ratio of compound X to the total mass of aromatic compounds is preferably 1% by mass or more, for example 2% by mass or more, and the upper limit can be 20% by mass or less, or 18% by mass or less, or for example 15% by mass or less. Furthermore, from the viewpoint of obtaining high fluidity and resistance to material separation, the content ratio of compound X to the total mass of all monomers constituting the lignin derivative of the present invention (lignin sulfonic acid compound, aromatic compound, and aldehyde compound) is preferably 0.1% by mass or more, for example 1% by mass or more, and the upper limit can be 15% by mass or less, or 10% by mass or less.

[0037] <Other Aromatic Compounds> In the lignin derivative of the present invention, the aromatic compound may include, in addition to compound X, compound A, and compound B, other aromatic compounds that can react with these compounds, to the extent that they do not impair the effects of the present invention. Other aromatic compounds include, but are not limited to, phenol, bisphenol A, isophthalic acid, oxynaphthoic acid, benzoic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, cresolsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, hydroxyethylphenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,5-xylenol, 3,4-xylenol, 4-ethylphenol, catechol, p-tert-amylphenol, p-octylphenol, p-phenylphenol, p-tert-butylphenol, o-tert-butylphenol, m-tert-butylphenol, 2,6-(di-)tert-butylphenol, and 4-cyclohexyl Examples include phenol, 4-benzylphenol, 4-tritylphenol, p-methoxyphenol, p-butoxyphenol, 3-dimethylaminophenol, p-acetamidophenol, 4-methylsulfonylphenol, p-(1-imidazolyl)phenol, 4-hydroxybenzenesulfonamide, 4-hydroxythiobenzamide, 4-methylthiophenol, sesamol, 4-ethoxyphenol, 4-propylphenol, 4-allylphenol, 4-hydroxyacetanilide, 4-isopropylphenol, 4-vinylphenol, 1-naphthol, 4-amylphenol, 4-butylphenol, 2,6-di-tert-butyl-p-cresol, 4-hexylphenol, 4-heptylphenol, 4-nonylphenol, 2-hydroxyanthracene, 4-dodecylphenol, aniline, etc. If other aromatic compounds are included, their content may be less than 10% by mass, for example, less than 5% by mass, relative to the total mass of aromatic compounds.

[0038] <Aldehyde Compounds> As the aldehyde compound, compound C having the structure represented by the following formula (3) can be preferably used. In the formula, R ４ R 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. These alkyl groups, alkenyl groups, phenyl groups, naphthyl groups, and heterocyclic groups may be substituted with any substituent such as alkyl groups having 1 to 10 carbon atoms; aryl groups such as phenyl groups and naphthyl groups; halogen atoms such as chlorine atoms and bromine atoms; sulfonic acid functional groups such as sulfo groups and sulfonic acid bases; acyl groups such as acetyl groups; hydroxyl groups; amino groups; and carboxyl groups. ４ The alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms in the above compound A (formula (1)) may have a branched structure or a cyclic structure, and a specific example thereof is R １ Among the groups listed as specific examples of alkyl groups having 1 to 24 carbon atoms and alkenyl groups having 2 to 24 carbon atoms, alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms can be mentioned. Furthermore, examples of heterocyclic groups include furyl groups, thienyl groups, pyridyl groups, piperidyl groups, morpholino groups, etc. Also, r preferably represents a number from 2 to 100.

[0039] Compound C (aldehydes) include, for example, 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 acid, benzylaldehyde [(C ６ H ５) ２ Examples include C(OH)-CHO, naphthaldehyde, and furfural, but among these, the group consisting of formaldehyde, paraformaldehyde, benzaldehyde, and any mixture of two or more of these can be selected. Compound C can be used as a pure crystalline or powdery substance, or as a hydrate thereof, or in the form of an aqueous solution such as formalin, in which case the measurement or mixing of the components can be simplified.

[0040] Compound C, represented by formula (3) above, can be used individually or in combination of two or more types.

[0041] <Reaction Ratio of Each Compound> In the present invention, the reaction ratio of the ligninsulfonic acid compound and the aromatic compound is not particularly limited, but preferably, the mass ratio of the ligninsulfonic acid compound to the aromatic compound is 1:99 to 99:1. From the viewpoint of achieving both a high biomass content and fluidity and resistance to material separation of the hydraulic composition, for example, it can be 10:90 to 90:10, or for example, 20:80 to 75:25, or for example, 20:80 to 60:40. Furthermore, if the mass ratio of the ligninsulfonic acid compound to the aromatic compound is 20:80 to 55:45, it can be expected that more stable and high fluidity can be obtained, and in particular, if it is 25:75 to 55:45, it can be expected that even more stable and high fluidity and resistance to material separation can be obtained. Furthermore, the reaction amount of the aldehyde compound relative to the total amount of the ligninsulfonic acid compound and aromatic compound is not particularly limited, but preferably, the total amount and the aldehyde compound are expressed by mass ratio, preferably the total amount of the ligninsulfonic acid compound and aromatic compound : aldehyde compound = 99:1 to 80:20, more preferably 98:2 to 85:15, for example 98:2 to 90:10.

[0042] <Lignin Derivatives and Methods for Producing the Same> The lignin derivative of the present invention is a reaction product of a mixture containing the above-mentioned ligninsulfonic acid compound, aromatic compound, and aldehyde compound, and comprises a copolymer obtained by polycondensation of these mixtures. The polymerization method for obtaining the above copolymer is not particularly limited. Furthermore, the order and method of adding the above-mentioned ligninsulfonic acid compound, aromatic compound, and aldehyde compound during polycondensation are not particularly limited. For example, the entire amount of these raw material compounds may be added at once before the polycondensation reaction, a portion of the raw material compounds may be added before the polycondensation reaction and then the remainder may be added dropwise in installments, or a portion 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 the aromatic compound and aldehyde compound before the reaction before polycondensation and then adding the ligninsulfonic acid compound dropwise in installments to this mixture, it is expected that the molecular weight of the resulting copolymer can be easily controlled.

[0043] Lignin derivatives can be obtained, for example, by polycondensing lignin sulfonic acid compounds, aromatic compounds, and aldehyde compounds in the presence of a dehydrating catalyst, either in a solvent-free or solvent-based manner, at a reaction temperature of 80°C to 150°C, under atmospheric pressure to pressurized pressure, for example, 0.001 to 1 MPa. Examples of the above-mentioned dehydration catalysts 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, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, etc. These dehydration catalysts can be used individually or in combination of two or more types. Furthermore, when carrying out the polycondensation reaction under 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 cyclic aliphatic compounds such as methylcyclohexane. In addition, any solvent suitable as a dehydration catalyst (acid catalyst), such as acetic acid, can also be used. When carrying out the polycondensation reaction under a solvent, the concentration of the components used in the polycondensation reaction (ligninsulfonic acid compounds, aromatic compounds, and aldehyde compounds) in the reaction system can be appropriately selected. However, if the concentration is too high, gelation is likely to occur, and if it is too low, the reaction may not proceed quickly. For example, the components used in the polycondensation reaction can be set to about 30-70%. The reaction temperature can be, for example, 95°C to 130°C, and the polycondensation reaction can be completed by reacting for about 3-25 hours. The polycondensation reaction is preferably carried out under acidic conditions, and it is desirable to set the pH of the reaction system to 4 or less. Furthermore, an antifoaming agent may be used during the production of lignin derivatives (during the polycondensation reaction). This suppresses foaming during the reaction and allows for the construction of a homogeneous reaction system.

[0044] After the polycondensation reaction is complete, various conventionally known methods can be used to reduce the content of unreacted aldehyde components (compound C) in the reaction system. For example, methods include making the pH of the reaction system alkaline and heating it to 60-140°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 bisulfite, hydrogen peroxide, ethylene urea 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, but even if the catalyst is not removed, the performance of the present invention as an additive for hydraulic compositions, as described later, will not be impaired. Methods for catalyst removal other than filtration include phase separation, dialysis, ultrafiltration, and the use of ion exchangers. Furthermore, neutralizing the reaction products and diluting them with water, etc., improves the workability of metering and other operations when used as an additive for hydraulic compositions, as described later. In this case, examples of basic compounds used for neutralization include alkaline hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, and organic amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. One or more of these may be used in combination. For example, sodium hydroxide and calcium hydroxide can be used in combination as basic compounds for neutralization.

[0045] The copolymer ultimately obtained has a suitable weight-average molecular weight Mw (calculated by gel permeation chromatography (hereinafter referred to as "GPC method"), in terms of polyethylene glycol) in the range of 4,000 to 150,000, and more preferably in the range of 8,000 to 120,000, particularly in the range of 12,000 to 100,000, from the viewpoint of exhibiting excellent dispersion performance. In this invention, the "lignin derivative" may consist only of copolymers obtained by polycondensation of monomer mixtures containing lignin sulfonic acid compounds, aromatic compounds, and aldehyde compounds, but generally, it also includes unreacted components and by-reactants generated in each polymerization step, alkylene oxide addition step, etc.

[0046] <Additives for Hydraulic Compositions> The additives for hydraulic compositions of the present invention contain the lignin derivative described above. Depending on the application, known and used additives for hydraulic compositions can also be appropriately adopted and combined, and used in the form of so-called admixtures. Specifically, at least one other additive selected from the group consisting of conventionally known cement dispersants, high-performance AE water-reducing agents, high-performance water-reducing agents, AE water-reducing agents, water-reducing agents, air-entraining agents (AE agents), foaming agents, defoaming agents, setting retarders, setting accelerators, separation reducing agents, thickeners, shrinkage reducing agents, curing agents, water-repellent agents, etc., can be blended. In the present invention, a hydraulic composition refers to a composition containing powders that harden by a hydration reaction (hydraulic powders), such as cement, gypsum, fly ash, blast furnace slag, etc. When the hydraulic powder is cement, the hydraulic composition is also called a cement composition.

[0047] Generally, cement dispersants are used in appropriate combinations depending on the manufacturing conditions and performance requirements of the concrete. The same applies to the additive for hydraulic compositions of the present invention; it is used alone or as the main component of the cement dispersant, but it can also be used as a modifying aid for cement dispersants with high slump loss, or in combination with cement dispersants with high initial water-reducing properties. For example, known cement dispersants include salts of polycarboxylic acid copolymers described in Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, etc., as well as salts of naphthalene sulfonic acid formalin condensate, salts of melamine sulfonic acid formalin condensate, lignin sulfonate, sodium gluconate, and sugar alcohols. The mixing ratio (mass ratio) of the lignin derivative of the present invention and known cement dispersants is, for example, lignin derivative:known cement dispersant = 1:99 to 99:1.

[0048] Examples of air entrainers include anionic air entrainers, nonionic air entrainers, and amphoteric air entrainers. Examples of coagulation retarders include inorganic coagulation retarders and organic coagulation retarders. More specifically, examples include oxycarboxylic acids and their salts such as gluconic acid, glucoheptonic acid, tartaric acid, citric acid, malic acid, and arabonic acid; sugars such as sucrose; and inorganic compounds such as zinc oxide, zinc chloride, silicic acid fluoride, and silicic acid fluoride salts. Examples of accelerators include inorganic accelerators and organic accelerators. Examples of thickeners and separation reducers include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymer-based thickeners such as deutan gum, welan gum, and xan gum, and nonionic thickeners such as polyethylene glycol and polyalkylene oxide. Examples of defoamers include nonionic defoamers, silicone-based defoamers, higher alcohols, and mixtures mainly composed of these.

[0049] When the hydraulic composition additive of the present invention is applied, for example, to a cement composition, the components constituting the cement composition are conventional concrete components, and can include cement (e.g., ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, low-heat / moderate-heat Portland cement, or blast furnace cement), aggregate (i.e., fine aggregate and coarse aggregate), admixture (e.g., silica fume, calcium carbonate powder, blast furnace slag fine powder, fly ash, etc.), expansive agent, and water. Furthermore, the hydraulic composition additive of the present invention is useful as an additive for hydraulic compositions containing not only natural aggregates such as river sand and river gravel, mountain sand and mountain gravel, land sand and land gravel, and sea sand, but also artificial aggregates such as crushed stone, crushed sand, crushed stone powder, and blast furnace slag fine aggregate.

[0050] Furthermore, the hydraulic composition additive of the present invention can also be suitably used in hydraulic compositions (cement compositions) that include fly ash or blast furnace slag fine powder as admixtures. Fly ash is silica (SiO ２ ), alumina (Al ２ O ３)is the main component, 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-entraining agent used, and that an increase in the amount of unburned carbon tends to lead to an increase in the amount of air-entraining agent used. The amount of unburned carbon is generally considered to correlate with the amount of methylene blue adsorbed by fly ash. Blast furnace slag fine powder is a byproduct of refining iron in a blast furnace, and is composed of calcium oxide (CaO) and silica (SiO₂ ２ ), alumina (Al ２ O ３ It mainly consists of ) and its standard is specified in JIS A 6206.

[0051] In addition, admixtures other than the additives for hydraulic compositions of the present invention that can be added separately during formulation include the aforementioned publicly known and used air-entraining agents, setting retarders, setting accelerators, separation reducing agents, thickeners, defoaming agents, shrinkage reducing agents, etc., which can also be blended as appropriate. The blending ratio of each of these components can be appropriately determined depending on the type of selected component and its intended use.

[0052] The amount of the hydraulic composition additive of the present invention varies depending on the mixing conditions, including the materials of the concrete described above. However, it is usually added in an amount of approximately 0.05 to 5.0% by mass (as the amount of the lignin derivative itself) relative to the mass of cement, or, in the case of using pozzolanic fine powder such as fly ash in combination, relative to the total mass of cement and the powder such as fly ash, on a solid content basis. The amount added is adjusted appropriately according to the desired initial flow value, but care must be taken as adding too much may cause delayed setting and, in some cases, lead to poor hardening. Furthermore, in concrete manufacturing control, it is desirable that the additive is less affected by fluctuations in the quality of fine aggregate and that there is less variation in the amount added to obtain the desired slump and slump flow. The hydraulic composition additive of the present invention can achieve higher fluidity than conventional products, meaning that it can exhibit performance at a lower addition rate compared to conventional products. The method of use is the same as for general cement dispersants; it can be added undiluted during concrete mixing, or diluted in the mixing water beforehand and then added. Alternatively, it can be added after mixing the concrete or mortar and then mixed uniformly again.

[0053] The present invention will be described below with reference to examples. However, the present invention is not limited in any way by these examples and comparative examples.

[0054] 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 sodium nitrate aqueous solution and acetonitrile (volume ratio 80 / 20) Detector: Differential refractometer, Calibration curve: Polyethylene glycol

[0055] [Production Example 1] (Preparation of Aromatic Compound A) Three moles of a 6-mol ethylene oxide (EO) adduct of p-tert-butylphenol were charged into a glass reaction vessel equipped with a stirrer, thermometer, and nitrogen inlet tube. One mole of phosphoric anhydride was charged at 50°C over four hours while nitrogen bubbling was performed, and the reaction was carried out. Subsequently, a maturation reaction was carried out at 100°C for three hours to complete the phosphate esterification reaction, and the phosphate ester of the 6-mol p-tert-butylphenol EO adduct (A-1) was obtained. Similarly, phosphate esters of the 90-mol EO adduct of p-tert-butylphenol (A-2), the 44-mol EO adduct of p-tert-butylphenol (A-3), the 22-mol EO adduct of p-tert-butylphenol (A-4), the 4-mol EO adduct of bisphenol A (A-5), the 3-mol EO adduct of p-tert-butylphenol (A-6), and the 3-mol EO adduct of phenol (A-7) were obtained. (Aromatic compound B) As aromatic compound B, poly(ethylene oxide) monophenyl ethers with various EO adduct moles, the 60-mol EO adduct of bisphenol A, and the 22-mol EO adduct of p-tert-butylphenol were prepared.

[0056] Furthermore, the following compounds were used as aromatic compound X: (Aromatic compound X) X-1: p-hydroxybenzenethiol X-2: p-phenolsulfonic acid X-3: p-aminophenol X-4: tyrosine X-5: phenylphosphonic acid X-6: p-hydroxybenzoic acid X-7: anilinesulfonic acid

[0057] [Example 1] (Production of lignin derivative (L-1)) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device, 106 g of water, 2.3 g of aromatic compound A-1 synthesized in Production Example 1, 33.5 g of A-2, 35.1 g of sodium ligninsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.9 g of p-hydroxybenzenethiol (X-1) (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.1 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of the defoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged, 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 the reaction was complete, 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 hour. By filtering the mixture to remove the gypsum produced by neutralization, a liquid lignin derivative (L-1) containing a copolymer with a weight-average molecular weight of 51,900 was obtained.

[0058] [Example 2] (Production of lignin derivative (L-2)) Except that A-3 was used instead of phosphate ester compound A-2 as aromatic compound A, and p-aminophenol (X-3) was used instead of p-hydroxybenzenethiol, a liquid lignin derivative (L-2) containing a copolymer with a weight-average molecular weight of 52,100 was obtained under the same conditions and methods as in Example 1.

[0059] [Example 3] (Production of lignin derivative (L-3)) A liquid lignin derivative (L-3) containing a copolymer with a weight-average molecular weight of 53,300 was obtained under the same conditions and methods as in Example 1, except that A-6 was used instead of phosphate ester compound A-1, A-4 was used instead of A-2, and phenylphosphonic acid (X-5) was used instead of p-hydroxybenzenethiol as aromatic compound A.

[0060] [Example 4] (Production of lignin derivative (L-4)) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device, 106 g of water, 2.3 g of aromatic compound A-6 synthesized in Production Example 1, 39.0 g of EO 22 molar adduct of p-tert-butylphenol, 26.5 g of sodium ligninsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.9 g of p-hydroxybenzenethiol (X-1) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.7 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of the defoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged, 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 the reaction was complete, 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 hour. By filtering the mixture to remove the gypsum produced by neutralization, a liquid lignin derivative (L-4) containing a copolymer with a weight-average molecular weight of 49,300 was obtained.

[0061] [Examples 5-10] (Production of lignin derivatives (L-5 to L-10)) Liquid lignin derivatives (L-5) to (L-10) were obtained in the same manner as in Example 4, except that the types of lignin sulfonic acid compounds, aromatic compounds (A, B), and aromatic compound X, and the reaction ratios of each compound were changed as shown in Table 1.

[0062] [Example 11] (Production of lignin derivative (L-11)) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device, 106 g of water, 7.8 g of aromatic compound A-1 synthesized in Production Example 1, 30.4 g of poly(ethylene oxide) monophenyl ether (EO addition moles: 90), 30.4 g of sodium lignin sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of p-aminophenol (X-3) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.8 g of p-hydroxybenzoic acid (X-6) (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.2 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of the antifoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged, and the reaction vessel was heated to 105°C over 30 minutes under stirring. The reaction was carried out for 7 hours after the liquid temperature reached 105°C. After the reaction was complete, 42 g of 250 g / L calcium hydroxide aqueous solution and 7 g of 48% sodium hydroxide aqueous solution were added to the reaction vessel and stirred for another hour. By filtering these mixtures to remove the gypsum produced by neutralization, a liquid lignin derivative (L-11) containing a copolymer with a weight-average molecular weight of 49,300 was obtained.

[0063] [Example 12] (Production of lignin derivative (L-12)) A liquid lignin derivative (L-12) containing a copolymer with a weight-average molecular weight of 81,000 was obtained under the same conditions and methods as in Example 11, except that 11.7 g of A-7 was used instead of phosphate ester compound A-1 as aromatic compound A, 23.4 g of poly(ethylene oxide) monophenyl ether (number of EO added moles: 22) was used instead of the 90 EO adduct of phenol, 3.1 g of p-hydroxybenzenethiol (X-1) was used instead of p-aminophenol, and 3.1 g of p-hydroxybenzoic acid (X-6) was used.

[0064] [Example 13] (Production of lignin derivative (L-13)) A liquid lignin derivative (L-13) was obtained in the same manner as in Example 3, except that the reaction ratios of the lignin sulfonic acid compound, aromatic compound (A), and aromatic compound X were changed as shown in Table 1.

[0065] [Example 14] (Production of lignin derivative (L-14)) A liquid lignin derivative (L-14) was obtained in the same manner as in Example 12, except that the type of aromatic compound X was changed as shown in Table 1.

[0066] [Examples 15-17] (Production of lignin derivatives (L-15-L-17)) Liquid lignin derivatives (L-15) to (L-17) were obtained in the same manner as in Example 4, except that the types of lignin sulfonic acid compounds, aromatic compounds (A, B), and aromatic compound X, and the reaction ratios of each compound were changed as shown in Table 1.

[0067] [Comparative Example 1] (Production of Lignin Derivative (HL-1)) 106 g of water, 41.2 g of poly(ethylene oxide) monophenyl ether (EO addition moles: 100), 2.2 g of p-hydroxybenzoic acid (X-6), 4.9 g of aniline sulfonic acid (X-7), 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% sulfuric acid aqueous solution, and 0.02 g of the defoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged into a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux apparatus. 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 the reaction was complete, 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 hour. By filtering the mixture to remove the gypsum produced by neutralization, a liquid lignin derivative (HL-1) containing a copolymer with a weight-average molecular weight of 24,000 was obtained.

[0068] [Comparative Example 2] (Production of Lignin Derivative (HL-2)) A liquid lignin derivative (HL-2) was obtained in the same manner as in Comparative Example 1, except that the types of lignin sulfonic acid compounds and aromatic compounds, and the reaction ratios of each compound were changed as shown in Table 1.

[0069] [Comparative Example 3] Commercially available sodium lignin sulfonate (HL-3) was used in the test as is.

[0070]

[0071] [Fresh Mortar Test] <Materials and Mix Design>

[0072]

[0073] ≪Chemical Composition Analysis of Fine Aggregate≫ Ignition loss (ig loss) is the loss value at 950°C. Chemical composition was measured by X-ray fluorescence analysis (Rigaku Corporation, ZSX Primus IV). ≪Physical Property Tests of Fine Aggregate≫ Surface-dry density was measured according to JIS A 1109:2014. Sieving (coarseness ratio (F.M.) and 0.15 mm penetration) was performed according to JIS A 1102:2020. Water absorption rate was measured according to JIS A 1109:2014.

[0074] ≪Mixing Method≫ Fine aggregate (sand 1 to sand 4) and cement were added in the amounts listed in Table 2 to a high-power mixer (manufactured by Maruto Seisakusho Co., Ltd.), and dry mixing was performed for 10 seconds. Next, lignin derivatives L-1 to L-17, HL-1 to HL-2 obtained in Examples 1 to 17 and Comparative Examples 1 to 2, or sodium lignin sulfonate (HL-3) from Comparative Example 3, and water in which Pronal 753W (0.01% relative to cement) manufactured by Toho Chemical Industry Co., Ltd. was dissolved were added to the mixer, and the mixture was mixed at low speed for 30 seconds. After the mixer was stopped for 30 seconds, the mixture was mixed at high speed for an additional 60 seconds to produce mortar, which was then subjected to flow measurement. Here, the amount of L-1 to L-17 and HL-1 to HL-3 used relative to the cement (solid content addition rate) was determined in advance by trial mixing. The amount of fine aggregate used to achieve an initial mortar flow value of 200 ± 10 mm in each mix design was confirmed for each type of fine aggregate (Sand 1 to Sand 4) (see Table 4, relative to cement addition ratio). Regardless of the type of fine aggregate, those with small variations in the amount of lignin derivative / sodium lignin sulfonate added (L-1 to L-17, HL-1 to HL-3) (those with small variations in the relative to cement addition ratio listed in Table 4) are less affected by changes in the mortar mix design, and the desired mortar flow value can be obtained stably.

[0075] ≪Flow Measurement Method≫ The spread (flow value) of the mortar was measured using a mini slump cone (a conical cylinder with an inner diameter of 50 mm at the top, an inner diameter of 100 mm at the bottom, and a height of 150 mm) in accordance with JIS A 1171 "Test Method for Polymer Cement Mortar". The flow value of the test mortar after 60 minutes was divided by the flow value of the test mortar immediately after mixing (initial flow value) to obtain the 60-minute retention rate of the flow (%). The results obtained are shown in Table 4.

[0076] ≪Material Separation Resistance (1): Density Difference≫ Mortar for evaluating material separation resistance was prepared using the same procedure as the mortar used for the flow measurement described above. The mortar, immediately after mixing, was poured into a 500 ml cylinder and left to stand at room temperature for 30 minutes. After 30 minutes, 250 ml of the upper layer of mortar was carefully removed from the cylinder and filled into a 250 ml cylinder. Similarly, 250 ml of the lower layer of mortar was filled into a different 250 ml cylinder. For both the upper and lower layers of mortar, the density (g / ml) was calculated using the following formula. The difference between the density of the upper and lower layers was defined as the density difference after 30 minutes. The results are shown in Table 4. A smaller density difference after 30 minutes indicates higher material separation resistance. Formula: Density of mortar (g / ml) = Weight of mortar (g) / 250 (ml)

[0077] ≪Material Separation Resistance (2): Sand Settlement Test≫ The upper and lower layers of the mortar used in the material separation resistance test were passed through a 200-mesh sieve to wash away the cement paste with water, and only the sand (fine aggregate) was separated from the mortar. The separated sand was dried at 80°C for 24 hours, and its weight was measured to calculate the ratio of sand that settled in the lower layer of the mortar to the total weight of sand in the mortar (upper and lower layers). The results are shown in Table 4. The closer the sand settlement ratio is to 50%, the higher the material separation resistance can be evaluated. Formula: Sand settlement ratio (%) = Weight of sand separated from the lower layer (g) / Total weight of sand separated (g)

[0078]

[0079] As shown in Table 4, the mortars of Examples 1 to 17, to which the lignin derivative of the present invention was added, showed little variation in the cement addition ratio (standard deviation of 0.55 or less), regardless of the type of fine aggregate (sand 1 to sand 4). Furthermore, in all cases where any of the fine aggregates (sand 1 to sand 4) was used, the 60-minute retention rate of the mortar flow exceeded 65%, and was almost 70%, confirming that it exhibited high fluidity. In the technical field of hydraulic compositions such as cement and mortar, a general requirement for fluidity is the ability to maintain fluidity for about 30 to 60 minutes (retention performance), and the above results fully satisfy the performance requirements in this industry. In addition, the density difference after 30 minutes, which is an indicator of resistance to material segregation, was 0.005 or less, and the sand sedimentation rate was 50 to 52%, confirming that the mortar exhibited excellent resistance to material segregation. In this embodiment, it was observed that the resistance to material separation tended to improve as the reaction ratio of compound X increased, and that the retention performance tended to improve when two or more types of compound X were used in combination.

[0080] On the other hand, the mortars of Comparative Example 1, which contained a lignin derivative without compound A as an aromatic compound; Comparative Example 2, which contained a lignin derivative without compound A and compound X as aromatic compounds; and Comparative Example 3, which used a commercially available lignin derivative, showed greater variation in the cement addition ratio due to the change in fine aggregate compared to the mortar of the above example. The retention rate of mortar flow after 60 minutes was 65% or less, and none reached 70%. In some cases, the flow was so poor that it was not possible to measure the flow value. Furthermore, the density difference after 30 minutes was also larger than that of the mortar of the above example. Although the sand sedimentation rate was similar to that of the example when using a commercially available lignin derivative (Comparative Example 3), the other samples showed a larger sand sedimentation rate and inferior resistance to material separation.

Claims

1. A lignin derivative which is a reaction product of a mixture containing a lignin sulfonic acid compound, an aromatic compound (excluding the lignin sulfonic acid compound), and an aldehyde compound, the lignin derivative having a (poly)alkyleneoxy group with a terminal phosphorylated ester group, and the aromatic compound containing a compound X represented by the following formula (4). (In the formula, X ａ represents a group or atom selected from the group consisting of -SH, -CHO, -COOM ｘ , -SO ３ M ｘ , -NH ２ , -CN, -NO ２ , -P(O)(OM ｘ ), ２ and a halogen atom, or represents an organic group having 1 to 10 carbon atoms containing one or more of these groups and atoms, M ｘ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group or an alkanolammonium group, and X ｂ represents a group or atom selected from the group consisting of a hydrogen atom, -OH, -NH ２ , -NH(C ６ H ４ NH ２ ), and -NH(CO)CH ３ (however, X ａ and X ｂ are not the same group, and when X ｂ represents a hydrogen atom, X ａ represents -P(O)(OH) ２ ).).

2. The lignin derivative according to claim 1, wherein the compound X is a compound represented by the following formula (4-1). (In the formula, X ａ -SH, -NH ２ , -SO ３ H, -P(O)(OH) ２ , or -CH ２ CHNH ２ Represents COOH, X ｂ represents a hydrogen atom or -OH (however X ｂ When X represents a hydrogen atom, ａ ha-P(O)(OH) ２ It represents...).

3. The lignin derivative according to claim 1, wherein the content ratio of compound X to the total mass of the aromatic compound is 1% to 20% by mass.

4. The lignin derivative according to claim 1, wherein the aromatic compound further comprises compound A represented by the following formula (1). (In the formula, n represents 1 or 2, and when n represents 1, R １ A represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. １ O represents an alkylene oxy group with 2 to 4 carbon atoms, and m represents A １ X represents the average number of moles of O added, ranging from 1 to 300. １ represents a phosphate ester group, and when n represents 2, R １ is, -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ - represents A １ O represents an alkylene oxy group with 2 to 4 carbon atoms, and m represents A １ X represents the average number of moles of O added, ranging from 1 to 300. １ (This represents a phosphate ester group.) 5. The lignin derivative according to claim 3, wherein the content ratio of compound A to the total mass of the aromatic compound is 3% by mass or more.

6. The lignin derivative according to claim 1, wherein the aromatic compound further comprises compound B represented by formula (2). (In the formula, q represents 1 or 2, and when q represents 1, R ３ A represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. ２ O represents an alkylene oxy group with 2 to 4 carbon atoms, and p represents A ２ R represents the average number of moles added, ranging from 1 to 300. ２ R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms, and when q represents 2, R ３ is, -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ - represents A ２ O represents an alkylene oxy group with 2 to 4 carbon atoms, and p represents A ２ R represents the average number of moles added, ranging from 1 to 300. ２ (This represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.) 7. The lignin derivative according to claim 1, wherein the aldehyde compound is compound C represented by formula (3). (In the formula, R ４ (where 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.) 8. The lignin derivative according to claim 1, wherein the lignin derivative 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 60:

40.

9. An additive for hydraulic compositions containing the lignin derivative described in any one of claims 1 to 8.

10. The additive for hydraulic compositions according to claim 9, which is an additive for hydraulic compositions containing artificial aggregate.

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