Polyol composition for injection drug solution and injection drug solution composition

Abstract

Provided is a polyol composition which is for an injection drug solution and which comprises a polyol, a polyisocyanate trimerization catalyst, and a urethanation catalyst, wherein the polyol includes a polyether polyol having an average hydroxyl value of 150-350 mgKOH / g, the trimerization catalyst includes a quaternary ammonium salt, and the urethanation catalyst includes an aliphatic tertiary amine.

Description

Polyol composition for injection drug solution and injection drug solution composition

[0001] This disclosure relates to polyol compositions for injection solutions and injection solution compositions.

[0002] Injection chemical compositions are known as materials for stabilizing the soil properties of the ground (bedrock, etc.). Injection chemical compositions are used, for example, as void-filling materials to fill voids between structures such as tunnels, underground structures, and high-rise buildings and the surrounding ground, or to fill voids that occur within the ground, and as ground injection materials to reinforce and improve the ground by penetrating into weak ground.

[0003] In areas prone to water leakage and seepage, injection chemical compositions are used to reinforce the ground and stop seepage and leakage. For example, Patent Document 1 discloses a chemical composition containing a polyol, an imidazole-based catalyst, a trimerizing catalyst, and a crosslinking agent, wherein the polyol includes a polyether polyol, and the crosslinking agent includes at least one selected from primary amines and secondary amines.

[0004] Japanese Patent Publication No. 2024-65667

[0005] Patent Document 1 uses an imidazole-based catalyst, but our own investigations have revealed that using an imidazole-based catalyst delays foaming and hardening in water, and reduces the water-stopping capacity against groundwater seepage and leaks.

[0006] This disclosure is made in view of the above circumstances and aims to provide an injection chemical composition that rapidly foams and hardens in water and is less likely to cause water contamination during underwater foaming, and a polyol composition used in said injection chemical composition.

[0007] This disclosure provides at least the following [1] to

[13] : [1] A polyol composition for injection solutions comprising a polyol, a trimerization catalyst for a polyisocyanate, and a urethane catalyst, wherein the polyol comprises a polyether polyol having an average hydroxyl value of 150 to 350 mg KOH / g, the trimerization catalyst comprises a quaternary ammonium salt, and the urethane catalyst comprises an aliphatic tertiary amine. [2] The polyol composition for injection solutions according to [1], wherein the quaternary ammonium salt comprises a cation represented by the following formula (I). [In formula (I), R １ and R ２ Each of these independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ３ R represents a monovalent hydrocarbon group having 1 to 16 carbon atoms, which may have an ether group, a thioether group, a hydroxyl group, or a tertiary amino group. ４ R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ５ R represents a divalent hydrocarbon group having 1 to 16 carbon atoms. １ ~R ３Two or three of these may be bonded together to form a ring. [3] The polyol composition for injection solutions according to [1] or [2], wherein the quaternary ammonium salt comprises a carboxylate anion. [4] The polyol composition for injection solutions according to any one of [1] to [3], wherein the content of the quaternary ammonium salt is 0.1 to 2 parts by mass per 100 parts by mass of the polyol. [5] The polyol composition for injection solutions according to any one of [1] to [4], wherein the aliphatic tertiary amine comprises triethylenediamine. [6] The polyol composition for injection solutions according to any one of [1] to [5], wherein the content of the aliphatic tertiary amine is 0.3 to 3 parts by mass per 100 parts by mass of the polyol. [7] The polyol composition for injection solutions according to any one of [1] to [6], wherein the ratio of the content of the aliphatic tertiary amine to the content of the quaternary ammonium salt is 0.2 to 5 by mass. [8] The polyol composition for injection solutions according to any one of [1] to [7], wherein the number average molecular weight of the polyether polyol is 400 to 1000. [9] The polyol composition for injection solutions according to any one of [1] to [8], wherein the average number of hydroxyl groups of the polyether polyol is 1.8 to 3.4.

[10] The polyol composition for injection solutions according to any one of [1] to [9], further comprising a polyamine containing two or more groups selected from the group consisting of primary amino groups and secondary amino groups.

[11] The polyol composition for injection solutions according to any one of [1] to

[10] , further comprising a viscosity modifier.

[12] The injection solution composition comprising a first liquid comprising the polyol composition according to any one of [1] to

[11] , and a second liquid containing a polyisocyanate.

[13] The injection drug composition according to

[12] , wherein the polyisocyanate comprises at least one selected from the group consisting of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.

[0008] According to this disclosure, it is possible to provide an injection chemical composition that rapidly foams and hardens in water and is less likely to contaminate the water during foaming in water, and a polyol composition used in said injection chemical composition.

[0009] The following describes exemplary embodiments of this disclosure in detail. However, this disclosure is not limited to the embodiments described below. In this specification, numerical ranges indicated using "~" indicate a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Also, unless otherwise explicitly stated, the units of the numbers before and after "~" are the same. Furthermore, the upper and lower limits described individually can be combined in any way.

[0010] <Polyol Composition for Injection Solution> One embodiment of the present disclosure is a polyol composition for injection solution (hereinafter also simply referred to as "polyol composition") used in combination with a polyisocyanate, comprising a polyol, a trimerization catalyst for polyisocyanate, and a urethane catalyst, wherein the polyol comprises a polyether polyol having an average hydroxyl value of 150 to 350 mg KOH / g, the trimerization catalyst comprises a quaternary ammonium salt, and the urethane catalyst comprises an aliphatic tertiary amine.

[0011] The injection solution composition using the above polyol composition is used, for example, to solidify the ground by injecting it between a structure such as a tunnel, underground structure, or high-rise building and the ground (e.g., bedrock), or into the ground (e.g., bedrock), and allowing it to foam and harden.

[0012] The above polyol composition provides an injection solution composition that foams and hardens rapidly in water and is less likely to contaminate the water during foaming in water. In other words, the above polyol composition provides an injection solution composition with excellent water-stopping properties and water-contamination resistance. For this reason, the above polyol composition is suitably used as an injection solution composition for stabilizing the ground and stopping water seepage and leakage in areas prone to water leakage and groundwater seepage.

[0013] (Polyols) Polyols include polyether polyols having an average hydroxyl value of 150 to 350 mg KOH / g. Examples of polyether polyols include polyether polyols obtained by adding alkylene oxide to an initiator such as a polyhydric alcohol or polyhydric amine (reaction products of the initiator and alkylene oxide).

[0014] The number of hydroxyl groups in a polyhydric alcohol is two or more (for example, 2 to 5), and may be 3 to 4 from the viewpoint of further improving water-sealing properties and water-stain resistance. Examples of polyhydric alcohols include ethylene glycol, 1,4-butylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, diethylene glycol, 1,6-hexanediol, 1,8-octanediol, and glycerin. These may be used individually or in combination of two or more compounds.

[0015] The number of amino groups in the polyhydric amine is two or more (for example, 2 to 5), and may be 3 to 4 from the viewpoint of further improving water-sealing properties and water-stain resistance. Examples of polyhydric amines include ethylenediamine and diethylenetriamine. These may be used individually or in combination of two or more compounds.

[0016] Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. These may be used individually or in combination of two or more compounds.

[0017] Specific examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polytetramethylene glycol, N,N'-bis(2-hydroxypolyethoxy)ethylenediamine, polyether polyols obtained by adding the above alkylene oxide to glycerin, and polyether polyols obtained by adding the above alkylene oxide to alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, etc.).

[0018] Polyether polyols may contain propylene oxide units from the viewpoint of suppressing elution into water such as spring water. From the above viewpoint, it is preferable to use a polyether polyol obtained by adding an alkylene oxide containing propylene oxide to an initiator such as a polyhydric alcohol or a polyhydric amine, and it is more preferable to use a polyether polyol obtained by adding an alkylene oxide containing propylene oxide to glycerin.

[0019] The average hydroxyl value of polyether polyols is 150 to 350 mg KOH / g, and may be 180 mg KOH / g or more, 200 mg KOH / g or more, or 220 mg KOH / g or more from the viewpoint of obtaining better water-sealing properties, and may be 300 mg KOH / g or less, 280 mg KOH / g or less, or 260 mg KOH / g or less from the viewpoint of obtaining better water-stain resistance.

[0020] The average hydroxyl value of a polyether polyol represents the number of hydroxyl groups and equivalent amounts of potassium hydroxide in milligrams (mg) per gram of sample, and is measured in accordance with JIS K1557-1.

[0021] The number-average molecular weight of the polyether polyol may be between 400 and 1000. When the number-average molecular weight of the polyether polyol is 400 or higher, better water stain resistance tends to be obtained. When the number-average molecular weight of the polyether polyol is 1000 or lower, better water stagnation tends to be obtained. From these viewpoints, the number-average molecular weight of the polyether polyol may be 500 or higher, 550 or higher, 600 or higher, or 650 or higher, or 900 or lower, 800 or lower, or 750 or lower, or 500 to 900, 550 to 800, 600 to 750, or 650 to 750.

[0022] The number-average molecular weight of a polyether polyol is a value measured by the GPC method, for example, under the following conditions: [Conditions] ・Main unit: HLC-8220 (manufactured by Tosoh Corporation) ・Column: TSKgel G3000H HL + G2000H HL (two of each used connected together) ・Mobile phase: THF ・Detector: RI ・Column temperature: 40℃ ・Pump flow rate: 1.0 ml / min ・Injection volume: 100 μl ・Sample concentration: 0.5% (w / w) ・Standard substance: Polyether polyol obtained by adding propylene oxide to ethylene glycol, with a number-average molecular weight of 2000 and an average number of functional groups of 1.97

[0023] The average number of hydroxyl groups in a polyether polyol may be between 1.8 and 3.4. A polyether polyol with an average number of hydroxyl groups of 1.8 or higher tends to yield better water-sealing properties. A polyether polyol with an average number of hydroxyl groups of 3.4 or less tends to yield better water-stain resistance. From these perspectives, the average number of hydroxyl groups in a polyether polyol may be 2.4 or higher, 2.8 or higher, 3.2 or lower, 3.1 or lower, 2.4 to 3.2, or 2.8 to 3.1. The average number of hydroxyl groups in a polyether polyol is calculated as follows: (Average number of hydroxyl groups) = (Average hydroxyl value × Number-average molecular weight) / 56110

[0024] The polyether polyol content may be 80% by mass or more, 84% by mass or more, or 88% by mass or more from the viewpoint of obtaining better water-sealing properties, and may be 98% by mass or less, 95% by mass or less, or 92% by mass or less from the viewpoint of obtaining better water-stain resistance. From these viewpoints, the polyether polyol content may be 80-98% by mass, 84-95% by mass or 88-92% by mass. Note that the above content is based on the total mass of the polyol composition.

[0025] The polyol may contain other polyols other than polyether polyol as long as it does not inhibit the effects of the present disclosure. However, from the viewpoint of obtaining better water-stopping property and better water pollution resistance, the content of polyether polyol in the total amount of polyol may be 70 to 100% by mass, 80 to 100% by mass or 90 to 100% by mass.

[0026] From the viewpoint of obtaining better water-stopping property, the content of polyol may be 80% by mass or more, 84% by mass or more, or 88% by mass or more. From the viewpoint of obtaining better water pollution resistance, the content of polyol may be 98% by mass or less, 95% by mass or less, or 92% by mass or less. From these viewpoints, the content of polyol may be 80 to 98% by mass, 84 to 95% by mass, or 88 to 92% by mass. The above content is the content based on the total mass of the polyol composition.

[0027] (Trimerization catalyst) The trimerization catalyst is a catalyst that promotes the trimerization reaction of isocyanate and contains a quaternary ammonium salt. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion. The quaternary ammonium cation has a structure in which four organic groups are bonded to a nitrogen atom. The organic group is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The organic group may contain a heteroatom-containing group such as a hydroxyl group or an amino group. The four organic groups may be the same as or different from each other. The quaternary ammonium salt may be a single salt composed of one kind of cation and one kind of anion, or a mixture containing a plurality of kinds of cations and / or a plurality of kinds of anions.

[0028] From the viewpoint of more easily obtaining better water-stopping property and better water pollution resistance, the quaternary ammonium salt may contain a cation represented by the following formula (I).

[0029] In formula (I), R １ and R ２ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ３ represents a monovalent hydrocarbon group having 1 to 16 carbon atoms, which may have an ether group, a thioether group, a hydroxy group or a tertiary amino group, and R ４represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ５ represents a divalent hydrocarbon group having 1 to 16 carbon atoms. Two or three of R １ to R ３ may be bonded to each other to form a ring.

[0030] R １ to R ４ The monovalent hydrocarbon group represented by may be an aliphatic hydrocarbon group (e.g., an alkyl group or a cycloalkyl group) or an aromatic hydrocarbon group (e.g., an aryl group). However, the monovalent hydrocarbon group represented by R ３ may have an ether group, a thioether group, a hydroxy group or a tertiary amino group.

[0031] R １ and R ２ The monovalent hydrocarbon group represented by may be an aliphatic hydrocarbon group from the viewpoint of further improving the curability, and may be a linear aliphatic hydrocarbon group from the viewpoint of further improving the curability. The carbon number of the monovalent hydrocarbon group represented by R １ and R ２ may be 1 to 3 from the viewpoint of further improving the curability. As the monovalent hydrocarbon group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group and isopropyl group) is preferable from the viewpoint of obtaining more excellent curability, a linear alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group and n-propyl group) is more preferable, and a methyl group is even more preferable.

[0032] R ３ The monovalent hydrocarbon group represented by may be an aliphatic hydrocarbon group which may have an ether group, a thioether group, a hydroxy group or a tertiary amino group from the viewpoint of further improving the curability, and may be an aliphatic hydrocarbon group having a tertiary amino group from the viewpoint of further improving the curability. The tertiary amino group may be contained in the main chain of the hydrocarbon group. That is, a part of the tertiary carbon of the hydrocarbon group may be substituted with nitrogen. The carbon number of the monovalent hydrocarbon group represented by R ３ may be 1 to 12 or 1 to 8 from the viewpoint of further improving the curability.

[0033] R ３ The total number of ether groups, thioether groups, hydroxyl groups, and tertiary amino groups in the monovalent hydrocarbon group represented by may be 2 or less.

[0034] R ３ Specific examples of monovalent hydrocarbon groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 3-dimethylamino-1-propyl group, 6-dimethylamino-1-hexyl group, 2-(2-dimethylamino)ethoxyethyl group, 2,4-dimethyl-2,4-diazahexyl group, 3,6-dimethyl-3,6-diazaheptyl group, 2,4-dimethyl-2,4-diazaheptyl group, 2,5-dimethyl-2,5-diazadecyl group, 2-methyl-4-ethyl-2,4-diazaheptyl group, 3,6-dimethyl-3,6-diazadecyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, and the like.

[0035] R ４ From the viewpoint of further improving curability, this may be a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. Among hydrocarbon groups, from the viewpoint of obtaining better curability, alkyl groups having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group, and isopropyl group) are preferred, linear alkyl groups having 1 to 3 carbon atoms (methyl group, ethyl group, and n-propyl group) are more preferred, and a methyl group is even more preferred.

[0036] R ５ The divalent hydrocarbon group represented by may be an aliphatic hydrocarbon group (e.g., an alkylene group or a cycloalkylene group) or an aromatic hydrocarbon group (e.g., an arylene group). If the hydrocarbon group is an aliphatic hydrocarbon group, its carbon number may be 1 to 16, 1 to 12, 1 to 6, or 1 to 3. If the hydrocarbon group is an aromatic hydrocarbon group, its carbon number may be 6 to 16, 6 to 14, or 6 to 12.

[0037] R ５The divalent hydrocarbon group represented by may be an aliphatic hydrocarbon group from the viewpoint of further improving curability. The aliphatic hydrocarbon group is preferably an alkylene group from the viewpoint of further improving curability. ５ The number of carbon atoms in the divalent hydrocarbon group represented by may be 1 to 3 from the viewpoint of further improving curability. Among hydrocarbon groups having 1 to 3 carbon atoms, alkylene groups having 1 to 3 carbon atoms (methylene group, ethylene group, n-propylene group, and isopropylene group) are preferred from the viewpoint of obtaining better curability, linear alkylene groups having 1 to 3 carbon atoms (methylene group, ethylene group, and n-propylene group) are more preferred, and methylene groups are even more preferred.

[0038] Quaternary ammonium salts may contain a cation represented by the following formula (Ia) from the viewpoint of obtaining even better water-sealing properties and even better water-stain resistance.

[0039] R in equation (Ia) ３ This is synonymous with the above.

[0040] Specific examples of quaternary ammonium cations include tetramethylammonium ion, trimethyl(2-hydroxypropyl)ammonium ion, triethylmethylammonium ion, trimethylheptylammonium ion, and N-(2-hydroxyethyl)-N-(2-hydroxypropyl)-N-dimethylammonium ion.

[0041] Quaternary ammonium salts may contain anions derived from acids such as organic acids and inorganic acids, and may also contain anions derived from esters such as carbonate esters. The anions of quaternary ammonium salts may also be anions that do not fall into any of these categories (for example, hydroxyl ions). Examples of anions derived from organic acids include carboxylate anions. Examples of anions derived from inorganic acids include halide ions (fluoride ions, chloride ions, bromide ions, etc.), bicarbonate ions, carbonate ions, etc.

[0042] The quaternary ammonium salt may contain a carboxylate anion to further improve its compatibility with the polyol solution or polyisocyanate solution. That is, the quaternary ammonium salt may be a salt composed of a quaternary ammonium cation and a carboxylate anion. The number of carbon atoms in the carboxylate anion may be, for example, 1 to 12, 1 to 7, or 1 to 3. Specific examples of carboxylate anions include formate ions, acetate ions, 2-ethylhexanoate ions (octylate ions), laurate ions, cyclohexanecarboxylate ions, and pivalate ions. Among these, from the viewpoint of further improving the compatibility between the quaternary ammonium salt and the polyol solution or polyisocyanate solution, it is preferable that the quaternary ammonium salt contains at least one selected from the group consisting of 2-ethylhexanoate ions, formate ions, and acetate ions.

[0043] A preferred example of a quaternary ammonium salt is a quaternary ammonium salt composed of a cation represented by formula (I) and a carboxylate anion; a more preferred example of a quaternary ammonium salt is a quaternary ammonium salt composed of a cation represented by formula (Ia) and a carboxylate anion; and a further preferred example of a quaternary ammonium salt is a quaternary ammonium salt composed of a cation selected from the group consisting of tetramethylammonium ion, trimethyl(2-hydroxypropyl)ammonium ion, triethylmethylammonium ion, trimethylheptylammonium ion, and N-(2-hydroxyethyl)-N-(2-hydroxypropyl)-N-dimethylammonium ion, and a carboxylate anion. By using one or more of the above examples of quaternary ammonium salts, it is easier to obtain even better water-sealing properties and even better water-stain resistance. From the viewpoint of enhancing these effects, the carboxylate anion in the above examples is preferably an anion selected from the group consisting of 2-ethylhexanoate ion, formate ion, and acetate ion.

[0044] The content of the quaternary ammonium salt may be 0.1 to 2 parts by mass per 100 parts by mass of polyol. When the content of the quaternary ammonium salt is 0.1 parts by mass or more per 100 parts by mass of polyol, better strength tends to be obtained. When the content of the quaternary ammonium salt is 2 parts by mass or less per 100 parts by mass of polyol, better water-sealing properties and water-stain resistance tend to be obtained. From these viewpoints, the content of the quaternary ammonium salt may be 0.3 parts by mass or more, 0.6 parts by mass or more, or 1 part by mass or more per 100 parts by mass of polyol, or 1.5 parts by mass or less, 1.2 parts by mass or less, 0.9 parts by mass or less, or 0.6 parts by mass or less, or 0.3 to 1.5 parts by mass, 0.6 to 1.2 parts by mass, 1 to 1.2 parts by mass, 0.1 to 0.9 parts by mass, or 0.1 to 0.6 parts by mass.

[0045] The trimerizing catalyst may include other trimerizing catalysts besides quaternary ammonium salts, as long as they do not impair the effects of the present disclosure. However, the content of quaternary ammonium salts relative to the total amount of trimerizing catalyst may be 70-100% by mass, 80-100% by mass, or 90-100% by mass, from the viewpoint of obtaining better water-sealing properties and better water-stain resistance.

[0046] (Urethane catalyst) The urethane catalyst is a catalyst that promotes the reaction (urethane formation) between polyols and polyisocyanates, and contains an aliphatic tertiary amine.

[0047] Aliphatic tertiary amines are non-aromatic compounds that have a structure in which three aliphatic hydrocarbon groups are bonded to a nitrogen atom. Furthermore, aliphatic tertiary amines are compounds that do not contain quaternary ammonium cations and are clearly distinguished from quaternary ammonium salts.

[0048] The aliphatic hydrocarbon group bonded to the nitrogen atom of the aliphatic tertiary amine may be linear, branched, or have a cyclic structure. From the viewpoint of obtaining better curability, the aliphatic hydrocarbon group is preferably an alkyl group or an alkanediyl group. The number of carbon atoms in the aliphatic hydrocarbon group may be, for example, 1 to 8, 1 to 6, or 2 to 4. The aliphatic hydrocarbon groups may be the same or different from each other. The aliphatic hydrocarbon groups may be bonded to each other to form a ring.

[0049] Aliphatic tertiary amines may have multiple tertiary amino groups. For example, an aliphatic tertiary amine may have a structure in which multiple tertiary amino groups are bonded to each other via polyvalent aliphatic hydrocarbon groups (e.g., alkanediyl groups).

[0050] Examples of aliphatic tertiary amines include N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N'-tetramethylethylenediamine, 2-methyltriethylenediamine, hexamethyltriethylenetetramine, N,N'-bis[2-(dimethylamino)ethyl]-N,N'-dimethylethylenediamine, and triethylenediamine.

[0051] The content of the aliphatic tertiary amine may be 0.3 to 3 parts by mass per 100 parts by mass of polyol. When the content of the aliphatic tertiary amine is 0.3 parts by mass or more per 100 parts by mass of polyol, excellent defoaming properties and superior water stain resistance tend to be obtained. When the content of the aliphatic tertiary amine is 3 parts by mass or less per 100 parts by mass of polyol, superior water-sealing properties tend to be obtained. From these viewpoints, the content of the aliphatic tertiary amine may be 0.5 parts by mass or more or 0.8 parts by mass or more per 100 parts by mass of polyol, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, or 0.8 parts by mass or less, 0.5 to 2 parts by mass, 0.8 to 1.5 parts by mass, 0.3 to 1 part by mass, or 0.3 to 0.8 parts by mass.

[0052] The ratio of the aliphatic tertiary amine content to the quaternary ammonium salt content (aliphatic tertiary amine / quaternary ammonium salt) may be 0.2 to 5 by mass ratio. When the above ratio is 0.2 or higher, excellent defoaming properties and better water stain resistance tend to be obtained. When the above ratio is 5 or lower, better water sealing properties tend to be obtained. From these viewpoints, the above ratio may be 0.3 or higher, 0.4 or higher, 0.5 or higher, 1 or higher, 2 or higher, or 3 or higher, or 4 or lower, 3 or lower, 2 or lower, 1.5 or lower, or 1 or lower, or 0.3 to 4, 0.4 to 3, 0.5 to 2, 1 to 5, 2 to 5, 3 to 5, 0.2 to 1.5, or 0.2 to 1.

[0053] The urethane catalyst may contain other urethane catalysts other than aliphatic tertiary amines, as long as they do not impair the effects of the present disclosure. However, the content of imidazole-based catalysts (e.g., imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole) is preferably less than 0.1 parts by mass per 100 parts by mass of polyol, from the viewpoint of obtaining better water-sealing properties and better water-stain resistance. The content of aliphatic tertiary amines relative to the total amount of urethane catalyst may be 70 to 100% by mass, 80 to 100% by mass, or 90 to 100% by mass, from the viewpoint of obtaining better water-sealing properties and better water-stain resistance.

[0054] (Polyamine) The polyol composition may further contain a polyamine comprising at least two groups selected from the group consisting of primary amino groups and secondary amino groups. As a crosslinking agent, the polyamine contributes to improving initial viscosity, strength, watertightness, etc.

[0055] The total number of primary and secondary amino groups contained in the polyamine is two or more, and may be 2 to 4 or 2 to 3.

[0056] Examples of polyamines include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, neopentanediamine, 4,4'-methylenebis(cyclohexylamine), isophoronediamine, bis(aminomethyl)cyclohexane, 2,5- or 2,6-diaminomethylbicyclo[2,2,1]heptane, diaminocyclohexane, diethyltoluenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, xylylenediamine, phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, diethylenetriamine, 1,3,5-tris(aminomethyl)benzene, and 1,3,5-tris(aminomethyl)cyclohexane. As polyamines, polyoxyalkylenediamines obtained by converting the hydroxyl groups of polyoxyalkylene glycols, which are obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc., to amino groups; and polyoxyalkylentriamines obtained by converting the hydroxyl groups of polyoxyalkylentriols, which are obtained by addition polymerization of propylene oxide and / or ethylene oxide to glycerin, trimethylolpropane, etc., to amino groups can also be used. Among the above, when 4,4'-methylenebis(cyclohexylamine) is used, a better water-sealing result tends to be obtained.

[0057] The polyamine content may be 0.2 to 10 parts by mass per 100 parts by mass of polyol. When the polyamine content is 0.2 parts by mass or more per 100 parts by mass of polyol, better water-sealing properties tend to be obtained. When the polyamine content is 10 parts by mass or less per 100 parts by mass of polyol, better water-stain resistance tends to be obtained. From these viewpoints, the polyamine content may be 0.5 parts by mass or more, 1 part by mass or more, 1.5 parts by mass or more, or 2 parts by mass or more per 100 parts by mass of polyol, or 7 parts by mass or less, or 4 parts by mass or less, or 0.5 to 7 parts by mass, 1 to 4 parts by mass, 1.5 to 4 parts by mass, or 2 to 4 parts by mass.

[0058] (Viscosity modifiers) The polyol composition may further contain viscosity modifiers. Examples of viscosity modifiers include diethylene glycol dibutyl ether, ethylene glycol monophenyl ether, diethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, diisononyl phthalate, and diisobutyl phthalate.

[0059] The viscosity modifier content may be adjusted so that the viscosity of the polyol composition reaches the desired viscosity. For example, the viscosity modifier content may be 1 to 20% by mass, 2 to 15% by mass, or 3 to 10% by mass, based on the total mass of the polyol composition.

[0060] The viscosity of the polyol composition at 25°C may be 500 mPa·s or less, 350 mPa·s or less, or 250 mPa·s or less, from the viewpoint of improving injectability into voids and permeability. The viscosity of the polyol composition at 25°C may be 50 mPa·s or more, from the viewpoint of the miscibility between the polyol composition and the polyisocyanate. From these viewpoints, the viscosity of the polyol composition at 25°C may be, for example, 50 to 500 mPa·s, 50 to 350 mPa·s, or 50 to 250 mPa·s.

[0061] In addition to the components described above, the polyol composition may contain additives such as foam stabilizers, flame retardants, formaldehyde scavengers, plasticizers, antioxidants, antibacterial agents, and corrosion inhibitors, to the extent that they do not impair the effects of the present disclosure.

[0062] <Injection Solution Composition> Another embodiment of the present disclosure is an injection solution composition comprising a first liquid consisting of the polyol composition of the above embodiment and a second liquid containing a polyisocyanate.

[0063] From the viewpoint of reactivity with polyols, polyisocyanates may include at least one selected from the group consisting of diphenylmethane diisocyanate (hereinafter also referred to as "MDI") and polymethylene polyphenyl polyisocyanate (hereinafter also referred to as "polymeric MDI"). "MDI" encompasses various isomers of 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI. "Polymeric MDI" means MDI to which one or more phenyl groups having isocyanate groups are added via methylene groups, resulting in a number of isocyanate functional groups of three or more.

[0064] MDI may include 4,4'-MDI and at least one selected from the group consisting of 2,4'-MDI and 2,2'-MDI. The mass ratio of the total content of 2,4'-MDI and 2,2'-MDI to the content of 4,4'-MDI ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) may be 20 / 80 to 45 / 55, 30 / 70 to 45 / 55, or 35 / 65 to 40 / 60 from the viewpoint of improving strength.

[0065] The mass ratio of MDI to polymeric MDI (MDI / polymeric MDI) may be 30 / 70 to 75 / 25, 50 / 50 to 75 / 25, or 55 / 45 to 70 / 30, from the viewpoint of improving injectability and permeability into voids.

[0066] The MDI content may be 30-75% by mass, 50-75% by mass, or 55-70% by mass, based on the total mass of the polyisocyanate, from the viewpoint of improving injectability into voids and permeability.

[0067] From the viewpoint of improving strength, the polymeric MDI content may be 25-70% by mass, 25-50% by mass, or 30-45% by mass, based on the total mass of polyisocyanate.

[0068] Polyisocyanates may contain reaction products of active hydrogen-containing compounds with MDI, polymeric MDI, or mixtures thereof. Active hydrogen-containing compounds are compounds having active hydrogen-containing groups such as hydroxyl groups and amino groups, and examples include organic polyols such as ethylene glycol, butanediol, glycerin, trimethylolpropane, sorbitol, and sucrose, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, polyether polyols, and polyester polyols.

[0069] Polyisocyanates may include urethane-modified, allophanate-modified, biuret-modified, carbodiimide-modified, isocyanurate-modified, uretdione-modified, and the like as modified forms of MDI and polymeric MDI.

[0070] The isocyanate group content of the polyisocyanate (hereinafter also referred to as "NCO content") may be 20% by mass or more, 21% by mass or more, or 22% by mass or more, from the viewpoint of viscosity and curability of the polyisocyanate. The NCO content of the polyisocyanate may be 33% by mass or less, 32% by mass or less, or 31.5% by mass or less, from the viewpoint of foaming and curability. From the above viewpoint, the NCO content of the polyisocyanate may be 20 to 33% by mass, 21 to 32% by mass or 22 to 31.5% by mass.

[0071] The second liquid may consist solely of polyisocyanate, or it may consist of a composition (polyisocyanate composition) containing polyisocyanate and other components other than polyisocyanate. Examples of other components include the same components that may be included in the polyol composition described above. If the second liquid contains other components, the polyisocyanate content may be 80% by mass or more and less than 100% by mass, 85 to 99% by mass, or 90 to 98% by mass, based on the total mass of the second liquid.

[0072] The viscosity of the second liquid at 25°C may be 500 mPa·s or less, 350 mPa·s or less, or 250 mPa·s or less, from the viewpoint of improving injectability and permeability into voids. The viscosity of the second liquid at 25°C may be 50 mPa·s or more, from the viewpoint of miscibility with the first liquid. From these viewpoints, the viscosity of the second liquid at 25°C may be, for example, 50 to 500 mPa·s, 50 to 350 mPa·s, or 50 to 250 mPa·s.

[0073] In the injectable drug solution composition, the first liquid and the second liquid may exist separately or may be mixed together.

[0074] From the viewpoint of improving defoaming properties and water stain resistance, the first and second liquids may be used in a ratio of 80 to 300 volumes of the second liquid to 100 volumes of the first liquid. Similarly, from the viewpoint of improving defoaming properties and water stain resistance, the amount of the second liquid to 100 volumes of the first liquid may be 90 to 200 volumes or 100 to 150 volumes.

[0075] The injectable drug composition may contain other liquids in addition to the first and second liquids.

[0076] <Consolidated Body> Another embodiment of the present disclosure is a consolidated body comprising a foamed hardened product of the injection chemical composition of the above embodiment and a ground solidified with the foamed hardened product.

[0077] The solidified body can be obtained, for example, by injecting the injection chemical composition of the above embodiment between a structure such as a tunnel, underground structure, or high-rise building and the ground (e.g., bedrock), or into the ground (e.g., bedrock), and allowing it to foam and harden, thereby solidifying the ground with the foamed hardened material formed from the injection chemical composition.

[0078] The method for injecting the injection chemical composition into the ground is not particularly limited and can be carried out by conventionally known methods. For example, after mixing the first liquid and the second liquid of the injection chemical composition, the resulting mixture may be injected into the ground and the first liquid and the second liquid may react (foam and harden) in the ground to form a foamed hardened material. In this case, the first liquid and the second liquid may be mixed in the above-mentioned mixing ratio. The mixing of the first liquid and the second liquid may be performed immediately before injecting the composition into the ground.

[0079] <Soil Stabilization Method> Another embodiment of the present disclosure is a soil stabilization method using the injection chemical composition of the above embodiment. This method includes the steps of injecting the injection chemical composition of the above embodiment between a structure and the ground, or into the ground, and allowing it to foam and harden.

[0080] According to the above method, voids between the structure and the ground, or within the ground, are filled with the foamed hardened material of the injection chemical composition, or unstable ground is solidified with the foamed hardened material of the injection chemical composition, thereby forming the solidified body of the above embodiment and stabilizing the soil properties of the ground.

[0081] The ground into which the injection chemical composition is injected may contain water such as leaks, seepage, or groundwater. According to the above method, even if the ground contains water, contamination of the water is unlikely, and leakage due to delayed hardening is unlikely. Examples of structures include, but are not limited to, tunnels, underground structures, and high-rise buildings.

[0082] The embodiments of this disclosure will be described in detail below, but this disclosure is not limited to these embodiments. Unless otherwise specified, "parts" and "%" in the embodiments refer to mass.

[0083] The following raw materials were used in the following examples and comparative examples: • Polyol 1: Polyether polyol obtained by adding propylene oxide to glycerin (manufactured by Yoshika Chemical Co., Ltd., trade name: Puranol G307, average number of hydroxyl groups 3, number average molecular weight 700, average hydroxyl value 240 mg KOH / g) • Polyol 2: Polyether polyol obtained by adding propylene oxide to glycerin (manufactured by Yoshika Chemical Co., Ltd., trade name: Puranol G305, average number of hydroxyl groups 3, number average molecular weight 500, average hydroxyl value 336 mg KOH / g) • Polyol 3: Polyether polyol obtained by adding propylene oxide to glycerin (manufactured by Yoshika Chemical Co., Ltd., trade name: Puranol G303, average number of hydroxyl groups 3, number average molecular weight 300, average hydroxyl value 560 mg KOH / g) - Polyol 4: Polyether polyol obtained by adding propylene oxide to propylene glycol (manufactured by Sanyo Chemical Industries, trade name: Sannix PP-2000, average number of hydroxyl groups 2, number average molecular weight 2000, average hydroxyl value 56 mg KOH / g) - Polyisocyanate 1: MDI / polymeric MDI = 40 / 60 (peak area ratio (mass ratio)), mass ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI ([2,4'-MDI + 2,2'-MDI] / 4,4'-MDI) = 3 / 97, NCO content 31.0% by mass (manufactured by Tosoh Corporation, trade name: MR-200) • Catalyst 1: N-(2-hydroxyethyl)-N-(2-hydroxypropyl)-N-dimethylammonium acetate (Kao Corporation, Kaolizer No. 410) • Catalyst 2: 33% by mass dipropylene glycol solution of triethylenediamine (Tosoh Corporation, product name: TEDA-L33) • Catalyst 3: 1,2-dimethylimidazole (Tosoh Corporation, product name: TOYOCAT DMI) • Polyamine 1: 4,4'-methylenebis(cyclohexylamine) (Shenzhen Yexu Industrial Co., Ltd., product name: PACM) • Viscosity modifier 1: Diethylene glycol dibutyl ether (Toho Chemical Co., Ltd., product name: Highsolve BDB) • Flame retardant 1: Tri(chloropropyl) phosphate (Keika Chemical Co., Ltd., product name: TCPP)

[0084] <Examples 1-3, Comparative Examples 1-3> (Preparation of Polyol Composition (First Solution)) The raw materials listed in Table 1 were charged in the amounts (unit: parts by mass, total amount including solvent) listed in Table 1, and stirred for 30 minutes to obtain the polyol compositions (first solution) of Examples 1-3 and Comparative Examples 1-3, respectively. The viscosity of the obtained polyol compositions (first solution) at 25°C is shown in Table 1. The viscosity was measured using a B-type viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.), and the value 120 seconds after the start of measurement was taken as the measured value.

[0085] (Preparation of Polyisocyanate Composition (Second Solution)) Polyisocyanate 1 (95.2 parts by mass) and flame retardant 1 (4.8 parts by mass) were charged and stirred for 30 minutes to obtain the polyisocyanate composition (second solution) to be used in Examples 1 to 3 and Comparative Examples 1 to 3. The viscosity of the polyisocyanate composition (second solution) measured in the same manner as above at 25°C was 170 mPa·s.

[0086] (Free Foaming Test) Free foaming tests were conducted on the injection chemical compositions of the examples and comparative examples, and the curing time and foaming ratio were measured. In the free foaming test, the first liquid and the second liquid were adjusted to a liquid temperature of 20°C, 50 mL each were placed in a 500 mL cup, and mixed and stirred for 5 seconds at 400 rpm using a three-one motor, and then foamed and cured in the cup. Details of the various measurement items are shown below, and the measurement results are shown in Table 1.

[0087] [Curing Time] The curing time was defined as the time from when the first and second liquids were mixed and stirred until the surface of the mixture (foam) could be pressed with a rod and no indentation remained.

[0088] [Expansion Ratio] Calculated using the following formula. If the expansion ratio calculated using the formula below is 2.0 times or less, the expansion ratio is considered good. Expansion ratio (times) = Volume of the molded product (foamed hardened product) after expansion (cm³) ３ ) / Volume of the mixture before foaming (cm³) ３ )

[0089] (Underwater foaming test) Underwater foaming tests were conducted on the injection chemical compositions of the examples and comparative examples, and the gel time, rise time, water turbidity after foaming, and defoaming time were measured. In the underwater foaming test, the first and second liquids were adjusted to a liquid temperature of 25°C, and 50 mL each was placed in a 500 mL cup. Immediately after mixing and stirring for 5 seconds at 400 rpm using a three-one motor, 100 mL of the mixture was quickly added to another cup containing 500 mL of water, and the mixture and water in the cup were vigorously stirred with a stirring rod for 30 seconds to induce foaming and hardening. Details of the various measurement methods are shown below, and the measurement results are shown in Table 1.

[0090] [Gel Time] The gel time was defined as the time from when the first liquid and the second liquid were mixed and stirred until stringing began when a rod was pressed against the surface of the mixture (foam).

[0091] [Rise Time] The rise time was defined as the time from when the first liquid and the second liquid were mixed and stirred until the foaming height reached its maximum.

[0092] [Water Turbidity After Foaming] The turbidity of the water after the rise time was measured using a turbidimeter (TURBIDIMETER 2100N, manufactured by HACH).

[0093] [Defoaming Time] After the rise time had ended, 125 mL of water was placed in a 250 mL polyethylene bottle and left to stand at room temperature for 30 minutes. Then, with the bottle tightly sealed, it was shaken vigorously for 10 seconds and left to stand. The time (in seconds) from the time it took for the bubbles to disappear from the water surface after standing was defined as the defoaming time.

[0094] In the underwater foaming test described above, water stain resistance and watertightness were evaluated according to the criteria shown in Table 2. For water stain resistance, a rating of C was good, a rating of B was very good, and a rating of A was exceptionally good. For watertightness, a rating of B was good, and a rating of A was very good.

[0095]

[0096]

Claims

1. A polyol composition for injection solutions, comprising a polyol, a trimerization catalyst for polyisocyanate, and a urethane catalyst, wherein the polyol comprises a polyether polyol having an average hydroxyl value of 150 to 350 mg KOH / g, the trimerization catalyst comprises a quaternary ammonium salt, and the urethane catalyst comprises an aliphatic tertiary amine.

2. The polyol composition for injection solutions according to claim 1, wherein the quaternary ammonium salt comprises a cation represented by the following formula (I). [In formula (I), R １ and R ２ Each of these independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ３ R represents a monovalent hydrocarbon group having 1 to 16 carbon atoms, which may have an ether group, a thioether group, a hydroxyl group, or a tertiary amino group. ４ R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ５ R represents a divalent hydrocarbon group having 1 to 16 carbon atoms. １ ~R ３ Two or three of them may be joined together to form a ring.

3. The polyol composition for injection solutions according to claim 1, wherein the quaternary ammonium salt comprises a carboxylate anion.

4. The polyol composition for injection solutions according to claim 1, wherein the content of the quaternary ammonium salt is 0.1 to 2 parts by mass per 100 parts by mass of the polyol.

5. The polyol composition for injection solutions according to claim 1, wherein the aliphatic tertiary amine comprises triethylenediamine.

6. The polyol composition for injection solutions according to claim 1, wherein the content of the aliphatic tertiary amine is 0.3 to 3 parts by mass per 100 parts by mass of the polyol.

7. The polyol composition for injection solutions according to claim 1, wherein the ratio of the content of the aliphatic tertiary amine to the content of the quaternary ammonium salt is 0.2 to 5 by mass.

8. The polyol composition for injection solutions according to claim 1, wherein the number average molecular weight of the polyether polyol is 400 to 1000.

9. The polyol composition for injection solutions according to claim 1, wherein the average number of hydroxyl groups of the polyether polyol is 1.8 to 3.

4.

10. The polyol composition for injection solutions according to claim 1, further comprising a polyamine containing two or more groups selected from the group consisting of primary amino groups and secondary amino groups.

11. The polyol composition for injection solutions according to claim 1, further comprising a viscosity modifier.

12. An injectable drug composition comprising a first liquid consisting of a polyol composition according to any one of claims 1 to 11, and a second liquid containing a polyisocyanate.

13. The injectable drug composition according to claim 12, wherein the polyisocyanate comprises at least one selected from the group consisting of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.

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