Hydraulic composition, cured product, floor material, and urethanization catalyst

Abstract

To provide a hydraulic composition that can be fully cured to yield a cured product having excellent gloss.SOLUTION: A hydraulic composition comprises a urethanization catalyst, an active hydrogen-containing compound having more than one active hydrogen in one molecule (excluding the urethanization catalyst and water), a polyisocyanate compound having more than one isocyanate group in one molecule, a hydraulic cement, and water, wherein the urethanization catalyst is an amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2) (wherein R1 and R2 are each independently an organic group or a hydrogen atom): -C(CH3)2-NR1-C(CH3)2- (1-1) and -C(CH3)2-N(OR2)-C(CH3)2- (1-2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hydraulic composition, a cured product, a flooring material, and a urethanization catalyst. [Background technology]

[0002] Hydraulic compositions comprising a polyurethane resin and cement are known in the art, and the hardened products of the hydraulic compositions are used, for example, as flooring materials. Hydraulic compositions usually contain a polyisocyanate compound and an active hydrogen-containing compound as precursors of polyurethane resin, and also contain a urethanization catalyst to promote the reaction of these compounds. An amine catalyst is generally used as the urethanization catalyst.

[0003] Patent Document 1 discloses a polyurethane hydraulic composition using a tertiary amine compound such as dimethylaminoethanol as a catalyst. Patent Document 2 discloses a polyurethane hydraulic composition using a bis(morpholinoethyl) ether compound as a catalyst. Patent Document 3 discloses a polyurethane hydraulic composition using, as a catalyst, an imidazole compound in which the hydroxyl group on the 1-position N atom is not substituted with anything else. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-79820 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-117467 [Patent Document 3] JP 2016-196400 A Summary of the Invention [Problem to be solved by the invention]

[0005] Flooring materials are often required to have excellent gloss, such as a flow-type coating (with a smooth, high-gloss coating surface), but the gloss of the cured product of conventional hydraulic compositions does not fully satisfy such requirements. If the content of the urethane catalyst in the hydraulic composition is reduced, the gloss of the cured product increases, but the time required for the composition to fully cure after the start of curing increases.

[0006] The present invention provides a hydraulic composition that cures sufficiently to give a cured product having excellent gloss. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using an amine compound having a specific structure as a urethanization catalyst.

[0008] The present invention has the following aspects. [1] a urethane catalyst; an active hydrogen-containing compound having more than one active hydrogen per molecule (excluding the urethanization catalyst and water); a polyisocyanate compound having more than one isocyanate group per molecule; hydraulic cement; A hydraulic composition comprising: The hydraulic composition, wherein the urethanization catalyst is an amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2): -C(CH3)2-NR 1 -C(CH3)2- (1-1) -C(CH3)2-N(OR 2 )-C(CH3)2- (1-2) However, R 1 and R 2 are each independently an organic group or a hydrogen atom. [2] The hydraulic composition according to [1], wherein the amine compound is a hindered amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (2-1) and a structure represented by the following formula (2-2): [ka] However, R 1 and R 2 is as described above. * indicates a bond. [3] The hydraulic composition according to [1] or [2], wherein the amount of the urethane catalyst is 0.001 to 10 parts by mass per 100 parts by mass of the polyisocyanate compound. [4] The hydraulic composition of any one of [1] to [3], wherein the active hydrogen-containing compound is 5 to 5,000 parts by mass and the polyisocyanate compound is 10 to 200 parts by mass per 100 parts by mass of the hydraulic cement. [5] A hardened product of the hydraulic composition according to any one of [1] to [4]. [6] A flooring material made from the hardened material of [5] above. [7] A urethanization catalyst comprising an amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2): -C(CH3)2-NR 1 -C(CH3)2- (1-1) -C(CH3)2-N(OR 2 )-C(CH3)2- (1-2) However, R 1 and R 2 are each independently an organic group or a hydrogen atom. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a hydraulic composition that cures sufficiently to give a cured product having excellent gloss. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. In this specification, a structure, group, or compound represented by a chemical formula is also represented by a numbered structure, group, or compound of the formula. For example, a structure represented by formula (1-1) is also represented by structure (1-1). In this specification, the number average molecular weight (hereinafter also referred to as "Mn") is the polystyrene-equivalent molecular weight obtained by measurement by gel permeation chromatography (GPC) using a calibration curve prepared using standard polystyrene samples of known molecular weight.

[0011] [Hydraulic composition] The hydraulic composition of the present embodiment contains a urethane-forming catalyst which is a specific amine compound, an active hydrogen-containing compound, a polyisocyanate compound, hydraulic cement, and water. The hydraulic composition of the present embodiment may further contain other components in addition to those described above.

[0012] <Urethanization catalyst> The urethanization catalyst is an amine compound having at least one structure selected from the group consisting of the following structures (1-1) and (1-2). According to the investigations of the present inventors, an amine compound having this structure functions as a urethanization catalyst. By using this amine compound as a urethanization catalyst, the hydraulic composition is sufficiently cured, and a cured product having excellent gloss can be obtained.

[0013] -C(CH3)2-NR 1 -C(CH3)2- (1-1) -C(CH3)2-N(OR 2 )-C(CH3)2- (1-2) However, R 1 and R 2 are each independently an organic group or a hydrogen atom.

[0014] R 1 and R 2The organic group in the formula (I) may be, for example, a monovalent hydrocarbon group. The number of carbon atoms in the monovalent hydrocarbon group is, for example, 1 to 12, or preferably 1 to 8. The monovalent hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an aralkyl group. Among these, an alkyl group is preferred in terms of the degree of freedom of molecular motion. Of the structures (1-1) and (1-2), the structure (1-1) is preferred in terms of the degree of freedom of molecular motion.

[0015] It is preferable that N in the structure (1-1) and N in the structure (1-2) are N constituting the ring skeleton of a piperidyl group, since there are no inverted isomers. That is, it is preferable that the amine compound has at least one selected from the group consisting of a piperidyl group having the structure (1-1) (where N in the structure (1-1) is N constituting the ring skeleton of the piperidyl group) and a piperidyl group having the structure (1-2) (where N in the structure (1-2) is N constituting the ring skeleton of the piperidyl group). The amine compound is more preferably a hindered amine compound having at least one type (hereinafter also referred to as a hindered amine group) selected from the group consisting of the following structures (2-1) and (2-2).

[0016] [ka] However, R 1 and R 2 is as described above. * indicates a bond.

[0017] The amine compound may have one or more of at least one structure selected from the group consisting of the structure (1-1) and the structure (1-2) in one molecule. Amine compounds are preferred because of their superior electron donating properties. 1 is an organic group, and R 2is an organic group. 1 is a hydrogen atom and R 2 R may further have either one or both of the structures (1-2) in which R is a hydrogen atom. 1 is an organic group, and R 2 an amine compound having either one or both of the structures (1-2) in which R is an organic group; 1 is a hydrogen atom and R 2 may be used in combination with an amine compound having either one or both of the structures (1-2) in which is a hydrogen atom. The same applies when the amine compound is a hindered amine compound.

[0018] The amine compound may be non-polymeric or polymeric. An example of the non-polymeric amine compound is the following compound (A1). L-(X) m (A1) wherein X is structure (2-1) or structure (2-2), m is an integer of 1 or greater, and L is an m-valent group. When m is 2 or greater, the m Xs may be the same or different.

[0019] m is preferably an integer of 1 to 15, and more preferably an integer of 1 to 4. When m is 1, L is, for example, -OC(=O)-R 4 -C(=O)-OR 5 (However, R 4 is an alkylene group, and R 5 is a hydrogen atom or an alkyl group.) Examples of the alkyl group include an alkoxy group which may have a substituent, an acryloyloxy group, and a methacryloyloxy group. 4 The alkylene group has, for example, 1 to 16 carbon atoms. 5 The alkyl group has, for example, 1 to 8 carbon atoms. The alkoxy group has, for example, 1 to 16 carbon atoms. Examples of the substituent that the alkoxy group may have include alkoxysilyl groups such as triethoxysilyl groups. When m is 2, L is, for example, -OC(=O)-R 4 -C(=O)-O-(where R 4 is as defined above.) and -OC(=O)-O-. When m is 3 or more, L may be, for example, R 6 -(C(=O)-O) m - (where m is as above, and R 6 is an m-valent hydrocarbon group which may have a substituent. The number of carbon atoms in the m-valent hydrocarbon group is, for example, 1 to 36, and further 1 to 18. Examples of the substituent which the m-valent hydrocarbon group may have include substituted or unsubstituted aryl groups such as 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl group.

[0020] When the amine compound is the above-mentioned hindered amine compound, the hindered amine group content is preferably 0.3 or more, more preferably 0.5 or more. The upper limit of the hindered amine group content is not particularly limited, but is, for example, 0.7. The hindered amine group content is the value obtained by dividing the product of the number of hindered amine groups and the molecular weight of the hindered amine group by the molecular weight of the hindered amine compound. When the content of the hindered amine group is at least as large as the lower limit of the above range, the urethanization catalytic effect tends to be more excellent.

[0021] Specific examples of the amine compound include the following: Methyl sebacate (1,2,2,6,6-pentamethyl-4-piperidyl), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethylpiperidin-4-yl esters of fatty acids (C=12-21 and unsaturated C=18), Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, reaction products of bis(2,2,6,6-tetramethyl-4-piperidyl) decanedioate with 2-hydroperoxy-2-methylpropane and octane, bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate, bis[2,2,6,6-tetramethyl-1-(undecyloxy)piperidin-4-yl] carbonate, reaction products of 2-aminoethanol, cyclohexane and N-butyl-2,2,6,6-tetramethylpiperidin-4-amine-2,4,6-trichloro-1,3,5-triazine peroxide, butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, Reaction products of 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly({6-[(2,4,4-trimethylpentan-2-yl)amino]-1,3,5-triazine-2,4-diyl}[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexane-1,6-diyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]).

[0022] Commercially available amine compounds can be used. Commercially available products containing an amine compound having the structure (2-1) include, for example, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-40MP, ADK STAB LA-40Si (all manufactured by ADEKA Corporation), Tinuvin 111FD, Tinuvin 144, Tinuvin 292, Tinuvin 304, Tinuvin 405, Tinuvin 506, Tinuvin 607, Tinuvin 708, Tinuvin 809, Tinuvin 909, Tinuvin 1009, Tinuvin 111FD, Tinuvin 144, Tinuvin 292, Tinuvin 111FD ... Examples include in622SF, Tinuvin765, Tinuvin770DF, Chimassorb944FDL, Chimassorb2020FDL (all manufactured by BASF), TMPS-E (manufactured by Shin-Etsu Chemical Co., Ltd.), CHIGUARD353 (manufactured by Chitec), EVERSORB91FD, EVERSORB94, EVERSORB94FD (all manufactured by Eiko Chemical Co., Ltd.), and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide (manufactured by Tokyo Chemical Industry Co., Ltd.). Examples of commercially available products containing an amine compound having the structure (2-2) include ADK STAB LA-81 (manufactured by ADEKA Corporation), Tinuvin 123, Flamestat NOR116FF (all manufactured by BASF), CHIGUARD 101, CHIGUARD 115 (all manufactured by Chitec), N1,N3-bis(2,2,6,6-tetramethylpiperidin-4-yl)isophthalamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and EVERSORB 95 (manufactured by Eiko Chemical Industry Co., Ltd.).

[0023] <Active hydrogen-containing compounds> The active hydrogen-containing compound has more than one active hydrogen per molecule, and does not include the urethanization catalyst and water. The hydraulic composition may contain one or more active hydrogen-containing compounds. When one type is used, the active hydrogen-containing compound has two or more active hydrogens in one molecule. When two or more types are used, the average number of active hydrogens per molecule exceeds one.

[0024] The active hydrogen-containing compound is preferably a compound having a hydroxyl group or an amino group. A primary amino group has two active hydrogen atoms, and a secondary amino group has one active hydrogen atom. Examples of active hydrogen-containing compounds include alcohols, polyhydric alcohols, amines, alkanolamines, polyether monools, polyether polyols, polyester polyols, castor oil or derivatives thereof, and polybutadiene polyols.

[0025] The alcohol is preferably an alcohol having 1 to 6 carbon atoms, such as methanol, ethanol, propyl alcohol, isopropyl alcohol, and butanol. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. The amine is preferably an aliphatic amine, examples of which include ethylenediamine, diethylenetriamine, and triethylenetetramine. Examples of alkanolamines include monoethanolamine, N,N-dimethylaminoethanol, dimethylaminoethoxyethanol, N,N',N'-trimethyl-N-aminoethylethanolamine, diethanolamine, and triethanolamine.

[0026] The polyether monool is preferably a compound obtained by ring-opening addition of one or more alkylene oxides described below to the above alcohol as an initiator. The polyether polyol is preferably a compound obtained by ring-opening addition of one or more alkylene oxides described below to the above polyhydric alcohol or the above alkanolamine as an initiator. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. As the alkylene oxide, propylene oxide or a combination of propylene oxide and ethylene oxide is preferred.

[0027] The polyester polyol is preferably a compound obtained by reacting a polycarboxylic acid with one or more of the above polyhydric alcohols. Examples of the polycarboxylic acid include succinic acid, glutaric acid, pimelic acid, adipic acid, sebacic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, and terephthalic acid. Polyester diols obtained by reacting dicarboxylic acids with dihydric alcohols are more preferred.

[0028] From the viewpoints of hydrophobicity and reactivity, the active hydrogen-containing compound preferably contains one or more compounds selected from the group consisting of castor oil, castor oil derivatives, polyether polyols, and polyester polyols, and more preferably contains either or both of castor oil and castor oil derivatives.

[0029] The Mn of the active hydrogen-containing compound is preferably from 300 to 3,000, more preferably from 400 to 2,500, and even more preferably from 500 to 2,000, from the viewpoint of flowability. The average number of active hydrogen atoms per molecule of the active hydrogen-containing compound is preferably 2 to 5.

[0030] <Polyisocyanate compounds> A polyisocyanate compound has more than one isocyanate group in one molecule. The hydraulic composition may contain one or more types of polyisocyanate compounds. When one type is used, the polyisocyanate compound has two or more isocyanate groups in one molecule. When two or more types are used, the average number of isocyanate groups per molecule exceeds one. The polyisocyanate compound is preferably a low molecular weight polyisocyanate compound or an isocyanate group-terminated urethane prepolymer.

[0031] Examples of low molecular weight polyisocyanate compounds include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and modified products thereof. An example of the aliphatic diisocyanate is hexamethylene diisocyanate. Examples of alicyclic diisocyanates include 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and isophorone diisocyanate. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polyphenyl polyisocyanate (polymeric MDI), and xylylene diisocyanate. Examples of the modified products include uretidione modified products, nurate modified products, allophanate modified products, carbodiimide modified products, and biuret modified products.

[0032] The isocyanate group-terminated urethane prepolymer is preferably a compound obtained by reacting the low-molecular-weight polyisocyanate compound with a polyhydric alcohol under conditions that result in an excess of isocyanate groups. Examples of the polyhydric alcohol include the same polyhydric alcohols as those mentioned above as the active hydrogen-containing compound, and among these, polyether polyols are preferred. The Mn of the isocyanate group-terminated urethane prepolymer is preferably 500 to 10,000, more preferably 500 to 2,000.

[0033] As the polyisocyanate compound, from the viewpoints of reactivity and workability, the low molecular weight polyisocyanate compounds are preferred, aromatic diisocyanates or alicyclic diisocyanates are more preferred, and polymeric MDI is even more preferred.

[0034] <Hydraulic cement> Hydraulic cement hardens or sets upon mixing with water. Any known hydraulic cement can be used. Portland cement is preferred. Examples of Portland cement include ordinary Portland cement and high-early-strength Portland cement. From the viewpoints of reactivity and workability, ordinary Portland cement is preferred. White ordinary Portland cement (white cement) is more preferred because it is easy to adjust the color tone of the hardened product.

[0035] <Other ingredients> Examples of other components include aggregate, cement water reducing agent, plasticizer, antifoaming agent, carbon dioxide absorbent, and pigment.

[0036] As the aggregate, known inorganic aggregates or known organic aggregates can be used. One type of aggregate may be used, or two or more types may be used in combination. Examples of inorganic aggregates include natural siliceous materials such as river sand and silica sand, crushed inorganic materials such as glass, ceramics, fused alumina and silicon carbide, and hollow materials such as glass balloons and shirasu balloons. An example of the organic aggregate is crushed plastic. The aggregate may be colored with a dye or pigment.

[0037] The average particle size (median diameter based on number) of the aggregate is preferably 0.05 to 4 mm from the viewpoint of spreading workability. When two or more types of aggregate are used, it is preferable that the average particle size of each aggregate is within the above range. Fine glass, ceramics, and shirasu balloons with an average particle size of 0.05 mm or less may be used in combination as long as it does not impair spreading workability.

[0038] Cement water-reducing agents are components that act as surfactants to improve dispersion stability by acting on the interface between hydraulic cement particles and the dispersion medium. They also contribute to improving the fluidity, workability, and ease of application of hydraulic compositions. Known compounds can be used as cement water reducing agents, and specific examples include naphthalene sulfonate-formaldehyde condensate water reducing agents, melamine sulfonate-formaldehyde condensate water reducing agents, polycarboxylic acid water reducing agents, lignin sulfonic acid water reducing agents, polystyrene sulfonic acid water reducing agents, phenol formaldehyde condensate water reducing agents, and aniline sulfonic acid water reducing agents.

[0039] Examples of plasticizers include dioctyl phthalate, butyl benzyl phthalate, dioctyl adipate, diisononyl phthalate, glycol benzoate, alkylsulfonic acid phenyl ester, glycol octylic acid ester, diisononyl cyclohexane-1,2-dicarboxylate, and alkylsulfonic acid phenyl ester.

[0040] As the pigment, known inorganic pigments or known organic pigments can be used, and one type of pigment may be used, or two or more types may be used in combination. Examples of inorganic pigments include carbon black, titanium oxide, iron oxide, chromium oxide, and cobalt aluminate. The inorganic pigment may be subjected to a surface modification treatment to introduce a hydrophilic functional group. The introduction of the hydrophilic functional group improves the affinity with water, allowing the pigment to be stably dispersed in water. Examples of the hydrophilic functional group include a carboxy group, a sulfo group, a carbonyl group, and a hydroxy group. The hydrophilic functional group may form a salt.

[0041] The average primary particle size of the pigment is preferably 0.01 to 100.0 μm, more preferably 0.02 to 50.0 μm. When the particle size is equal to or greater than the lower limit of the above range, dispersion is facilitated and uniform color development is facilitated, and when the particle size is equal to or less than the upper limit, color vividness is facilitated. When two or more pigments are used in combination, it is preferable that the average primary particle size of each of them is within the above range. In this specification, the average primary particle size of a pigment is the volume-based median diameter measured by a particle size distribution analyzer using a laser diffraction method, for example, by measuring a sample diluted with water using a Microtrac MT3000 (manufactured by Microtrac Corporation).

[0042] <Content> The amount of the urethanization catalyst is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the polyisocyanate compound. When the amount is equal to or greater than the lower limit of the above range, the function of the urethanization catalyst is fully exerted, and the hydraulic composition is easily cured. When the amount is equal to or less than the upper limit, foaming due to rapid urethanization is suppressed, and the cured product is likely to have excellent gloss.

[0043] The amount of the active hydrogen-containing compound is preferably 5 to 5,000 parts by mass, more preferably 10 to 100 parts by mass, per 100 parts by mass of hydraulic cement. When the amount is equal to or greater than the lower limit of the above range, a good appearance of the cured product is likely to be obtained. When the amount is equal to or less than the upper limit, a good strength of the cured product is likely to be obtained.

[0044] The amount of the polyisocyanate compound is preferably 10 to 200 parts by mass, more preferably 50 to 100 parts by mass, per 100 parts by mass of hydraulic cement. When the amount is equal to or greater than the lower limit of the above range, good surface hardness of the cured product is likely to be obtained. When the amount is equal to or less than the upper limit, good fluidity of the hydraulic composition is likely to be obtained.

[0045] The amount of water is preferably 5 to 500 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of hydraulic cement. When the amount is equal to or greater than the lower limit of the above range, good fluidity of the hydraulic composition is likely to be obtained. When the amount is equal to or less than the upper limit, a good appearance of the set product is likely to be obtained.

[0046] When the hydraulic composition contains an aggregate, the amount of aggregate is preferably 10 to 10,000 parts by mass, more preferably 25 to 5,000 parts by mass, and even more preferably 100 to 1,000 parts by mass, per 100 parts by mass of hydraulic cement. When the amount is equal to or greater than the lower limit of the above range, a sufficient effect of suppressing cure shrinkage is likely to be obtained. When the amount is equal to or less than the upper limit, good spreading workability is likely to be obtained.

[0047] When the hydraulic composition contains a cement water-reducing agent, the amount of the cement water-reducing agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of hydraulic cement. When the amount is equal to or greater than the lower limit of the above range, good fluidity of the hydraulic composition is likely to be obtained. When the amount is equal to or less than the upper limit, good appearance of the set product is likely to be obtained.

[0048] <Method for producing hydraulic composition> The hydraulic composition is obtained by mixing a urethane catalyst, an active hydrogen-containing compound, a polyisocyanate compound, hydraulic cement, water, and, if necessary, other components.

[0049] The hydraulic composition hardens through the hydration reaction between the hydraulic cement and water, the urethane reaction between the active hydrogen-containing compound and the polyisocyanate compound, and the urea reaction between the polyisocyanate compound and water. Therefore, it is preferable that at least the mixing of the hydraulic cement with water, the mixing of the active hydrogen-containing compound with the polyisocyanate compound, and the mixing of the polyisocyanate compound with water be carried out at the construction site. The active hydrogen-containing compound and water may be mixed in advance.

[0050] Preferably, the hydraulic composition is produced by separately preparing a first composition containing an active hydrogen-containing compound and water, a second composition containing a polyisocyanate compound, a third composition containing hydraulic cement, and a urethanization catalyst, and mixing them together. The second composition is a liquid containing no water, and the third composition is a powder. When the hydraulic composition contains other components, the aggregate, carbon dioxide absorbent, and pigment are preferably contained in the third composition together with the hydraulic cement, and the cement water-reducing agent, plasticizer, and antifoaming agent are preferably contained in the first composition together with water.

[0051] The order in which the first to third compositions and the urethanization catalyst are mixed is not particularly limited. For example, the first to third compositions and the urethanization catalyst may be mixed all at once. Alternatively, the first composition, the second composition, and the urethanization catalyst may be mixed to prepare a premix, and the obtained premix may be mixed with the third composition.

[0052] <Hydraulic composition kit> The first to third compositions and the urethanization catalyst may be prepared in the form of a hydraulic composition kit. The hydraulic composition kit of this embodiment includes a first container containing the first composition, a second container containing the second composition, a third container containing the third composition, and a fourth container containing the urethane-forming catalyst. It is preferable to design the hydraulic composition so that a hydraulic composition of the desired composition can be obtained by mixing all of the components in each container, as this allows the components to be added at the construction site without measuring them and also provides excellent reproducibility in the amount of each component added.

[0053] The containers used for the first container and the second container may be any container that can contain and seal a liquid. An example is a bag-shaped container made of plastic film. The shape of the container is not particularly limited. For example, it may be a standing pouch shape that can stand upright when filled with liquid. The container used for the third container may be any container that can contain powder and has moisture-proof properties, such as a kraft paper bag for cement. The container used for the fourth container can be appropriately selected depending on the dosage form of the urethanization catalyst, which can be exemplified as a liquid, powder, or pellet.

[0054] <Method of manufacturing the cured product> After the hydraulic composition is produced, it is applied to an object to be worked on before hardening progresses, and then left to stand to obtain a hardened product. The application target can be, for example, a wall or floor of a building. A known application method can be applied depending on the application target. The application amount can be set depending on the thickness of the cured product to be obtained.

[0055] The cured product of the hydraulic composition is hard and has excellent abrasion resistance, heat resistance, chemical resistance, etc., and is suitable for flooring or wall materials. For example, it is suitable for flooring or wall materials in food factories, chemical factories, machine factories, etc., and is particularly suitable for flooring. In particular, it is suitable for poured type (with a smooth and high-gloss surface). The thickness of the flooring material made of the set product of the hydraulic composition is preferably set from the viewpoints of impact resistance, strength and design, and is preferably 1 to 50 mm, more preferably 2 to 20 mm, for example. [Example]

[0056] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the following examples. "Parts" and "%" mean "parts by mass" and "% by mass," respectively. Examples 1 to 7 are working examples, and Examples 8 to 13 are comparative examples.

[0057] [Evaluation method] <Hardness evaluation method> The hardness of the coating was measured using a Type D durometer 3 hours, 3.5 hours, and 4 hours after application of the hydraulic composition. The values ​​were recorded immediately after the pressure plate was brought into contact with the test piece and 5 seconds later. In the tables described below, the value after 5 seconds is shown in parentheses. If the value immediately after the pressure plate was brought into contact with the test piece was 0, it was considered "uncured." The hardness after 4 hours is preferably 50 or higher, and more preferably 60 or higher.

[0058] <Evaluation method for surface tack> Four hours after applying the hydraulic composition, the tester touched the surface of the coating with his fingertip to check for tackiness. If there was no tackiness, it was determined that the composition had cured sufficiently.

[0059] <Gloss evaluation method> The surface gloss of the cured product obtained in each example was measured using a gloss meter (Suga Test Instruments Co., Ltd., product number: HG-268, measurement angle: 60 degrees). The gloss is preferably 60 or higher, and more preferably 80 or higher.

[0060] [Materials used] Active hydrogen-containing compound 1: Castor oil, Mn approximately 840, average number of active hydrogen atoms per molecule 2.7. Polyisocyanate compound 1: Polyphenyl polyisocyanate (polymeric MDI), Mn approximately 630. Hydraulic cement 1: White Portland cement (white cement). Plasticizer 1: Butyl benzyl phthalate (anhydrous). Water reducer 1: Polycarboxylic acid-based water reducer (aqueous solution with 30% solids by mass). Antifoaming agent 1: Polysiloxane-based antifoaming agent (solid content 100% by mass). Pigment 1: LANXESS product name "COLORTHERM Green GN", chromium oxide pigment, average primary particle size 0.3 μm. Silica sand 1: Tohoku Silica Co. product name "No. 5 silica sand", average particle size 300 μm.

[0061] Catalyst 1: ADEKA product name "ADEKA STAB LA-82", 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (molecular weight: 239.36, number of structures (2-1): 1, hindered amine group content: 0.58). Catalyst 2: BASF product name "Tinuvin 292", a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 508.79, number of structures (2-1): 2, hindered amine group content: 0.55) and methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 369.54, number of structures (2-1): 1, hindered amine group content: 0.38). Catalyst 3: ADEKA product name "ADEKA STAB LA-72", main component: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 508.79, number of structures (2-1): 2, hindered amine group content: 0.55). Catalyst 4: ADEKA product name "ADEKA STAB LA-52", tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (molecular weight: 847, number of structures (2-1): 4, hindered amine group content: 0.66). Catalyst 5: ADEKA product name "ADEKA STAB LA-63P", a reaction product of 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol (molecular weight: approximately 2000, number of structures (2-1): 6, hindered amine group content: approximately 0.42). Catalyst 6: BASF product name "Tinuvin 144", butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] (molecular weight: 685, number of structures (2-1): 2, hindered amine group content: 0.41). Catalyst 7: Dimethylaminoethanol. Catalyst 8: 2-ethyl-4-methylimidazole. Catalyst 9: Bis(morpholinoethyl) ether. Here, the hindered amine group content is the value obtained by dividing the product of the number of hindered amine groups (structure (2-1), structure (2-2)) and the molecular weight of the hindered amine group by the molecular weight of the hindered amine compound.

[0062] [ka]

[0063] [Examples 1 to 13] According to the formulation shown in Tables 1 and 2, 1 active hydrogen-containing compound, 1 plasticizer, 1 water-reducing agent, 1 antifoaming agent, and water (additive water) were mixed with stirring to prepare a first composition. As a second composition, polyisocyanate compound 1 was prepared. As the third composition, 1 part hydraulic cement, 1 part pigment, and 1 part silica sand were mixed according to the formulation shown in Tables 1 and 2. 100 parts of the first composition, 100 parts of polyisocyanate compound 1, 500 parts of the third composition, and the amount (parts) of catalyst shown in Tables 1 and 2 were added to a stirring device (PRIMIX product name: Labo-lution), and the mixture was stirred at a rotation speed of 2500 rpm for a stirring time of 1 minute to obtain a hydraulic composition. The obtained hydraulic composition was applied to the entire surface of a white slate board (length 300 mm, width 300 mm) in an amount of 8 kg / m 2 The mixture was left to stand for 24 hours in an atmosphere at a temperature of 23°C and a humidity of 50% RH to obtain a cured product. The evaluation results of hardness, surface tack, and gloss are shown in Tables 1 and 2.

[0064] [Table 1]

[0065] [Table 2]

[0066] In Examples 1 to 7, the surfaces of the cured products were free of tack, and the hydraulic compositions were sufficiently cured within 4 hours after application. The cured products also had a high gloss of 70 or more. On the other hand, in Examples 8, 10, and 12, in which a different urethane catalyst was used instead of the amine compound having a specific structure, the gloss of the cured product was inferior. In Examples 9, 11, and 13, in which the amount of urethane catalyst was reduced compared to Examples 8, 10, and 12, the gloss was improved, but the surface of the cured product was tacky. [Industrial Applicability]

[0067] The hydraulic composition of the present invention contains an amine compound having a specific structure as a urethanization catalyst, and therefore cures sufficiently to give a cured product with excellent gloss.

Claims

1. a urethanization catalyst; an active hydrogen-containing compound having more than one active hydrogen per molecule (excluding the urethanization catalyst and water); a polyisocyanate compound having more than one isocyanate group per molecule; hydraulic cement; A hydraulic composition comprising: The hydraulic composition, wherein the urethanization catalyst is an amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2): -C(CH ３ ) ２ -NR １ -C(CH ３ ) ２ - (1-1) -C(CH ３ ) ２ -N(OR ２ )-C(CH ３ ) ２ - (1-2) However, R １ and R ２ are each independently an organic group or a hydrogen atom.

2. The hydraulic composition according to claim 1, wherein the amine compound is a hindered amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (2-1) and a structure represented by the following formula (2-2): 【Chemistry 1】 However, R １ and R ２ is as described above. * indicates a bond.

3. 2. The hydraulic composition according to claim 1, wherein the urethanization catalyst is 0.001 to 10 parts by mass per 100 parts by mass of the polyisocyanate compound.

4. 2. The hydraulic composition according to claim 1, wherein the active hydrogen-containing compound is 5 to 5,000 parts by mass and the polyisocyanate compound is 10 to 200 parts by mass relative to 100 parts by mass of the hydraulic cement.

5. A cured product of the hydraulic composition according to any one of claims 1 to 4.

6. A flooring material comprising the cured product according to claim 5.

7. A urethanization catalyst comprising an amine compound having at least one structure selected from the group consisting of a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2): -C(CH ３ ) ２ -NR １ -C(CH ３ ) ２ - (1-1) -C(CH ３ ) ２ -N(OR ２ )-C(CH ３ ) ２ - (1-2) However, R １ and R ２ are each independently an organic group or a hydrogen atom.

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