Chemical liquid composition and composition for filling gap

Abstract

To provide a composition for filling a gap, which comprises a composition (chemical liquid composition) containing a polyol and a composition containing a polyisocyanate, wherein there is sufficient time for these to come into contact and initiate the urethane reaction, allowing the foam to cure rapidly after expansion to yield a foam with low shrinkage, no brittleness, and excellent compressive strength and to provide a kit for filling a gap containing the composition for filling a gap.SOLUTION: The chemical liquid composition of the present invention is a composition which is used for preparing a composition for filling a gap in combination with a polyisocyanate, and contains a polyol and a catalyst, in which the polyol contains a low molecular weight polyol having an average molecular weight of 300 or less, the content ratio of the low molecular weight polyol is 70 mass % or more with respect to the total amount of the polyol, and the catalyst contains an imidazole compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a void-filling composition for forming a polyurethane resin foam in voids at civil engineering sites, construction sites, etc., and a chemical composition used for preparing the void-filling composition. In this specification, the term "void" refers to a space between two or more objects, a closed space, or the entire area from the opening to the bottom of a hole or the like, or the opening. [Background technology]

[0002] Conventionally, at civil engineering sites, construction sites, and the like, when voids impair the strength and stability of the ground or buildings, a construction method has been applied in which an agent that forms a foam made of polyurethane resin is supplied to the voids and then foamed and cured. For example, a caulking method using such an agent is known, in which an agent is supplied into an opening that leads from the surface to the interior of the ground to seal the opening, thereby forming a polyurethane resin foam. In this case, a method is applied in which an agent previously contained in a flexible container is subjected to foaming and curing to form a polyurethane resin foam at a predetermined position within the opening (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 9-221669 Summary of the Invention [Problem to be solved by the invention]

[0004] Chemicals used to form polyurethane resin foams typically consist of a polyol composition containing a polyol and a polyisocyanate composition containing a polyisocyanate. When using chemicals to form polyurethane resin foams at civil engineering or construction sites, if foaming and curing begin immediately upon contact between the polyol composition and the polyisocyanate composition when supplied to the void, sufficient working time cannot be ensured. Therefore, the composition of the chemicals must be adjusted to prevent insufficient supply to the entire target void. Furthermore, if a composition is used that slows the reaction rate in order to ensure sufficient working time, the time until curing increases, which can result in insufficient foaming in the space where the void is intended to be supplied or significantly slower curing. Therefore, a chemical that allows sufficient time for the urethane reaction to begin upon contact between the polyol composition and the polyisocyanate composition and rapidly cures after foaming is desired, regardless of the size of the intended supply area. Specifically, preferred properties required for such agents include a ratio (cream time / gel time) of 0.40 to 0.80 between the time from the start of mixing the polyol composition and the polyisocyanate composition until foaming begins (hereinafter referred to as "cream time") and the time from the start of mixing the polyol composition and the polyisocyanate composition until thickening occurs and gel strength begins to appear (resinization time; hereinafter referred to as "gel time").

[0005] One of the purposes of forming polyurethane resin foam in voids is to provide a waterproofing effect, so there is a demand for agents that can produce foams with little shrinkage, no brittleness, and excellent compressive strength.

[0006] An object of the present invention is to provide a void-filling composition comprising a polyol-containing composition (chemical composition) and a polyisocyanate-containing composition, which allows sufficient time for the urethane reaction to begin upon contact between the two, cures quickly after foaming, and provides a foam that has little shrinkage, is not brittle, and has excellent compressive strength, as well as a void-filling kit containing the same. Another object of the present invention is to provide a chemical composition for use in preparing such a void-filling composition. [Means for solving the problem]

[0007] The present invention is presented below. [1] A chemical composition used in combination with a polyisocyanate to prepare a void-filling composition, the chemical composition comprising a polyol and a catalyst, wherein the polyol comprises a low-molecular-weight polyol having an average molecular weight of 300 or less, the content of the low-molecular-weight polyol being 70 mass% or more relative to the total amount of the polyol, and the catalyst comprises an imidazole compound. [2] The liquid pharmaceutical composition according to the above [1], wherein the low-molecular-weight polyol comprises a first polyol having an average functionality of 2.5 or more. [3] The liquid pharmaceutical composition according to the above [1] or [2], wherein the low-molecular-weight polyol includes a second polyol having an average functionality of 2. [4] The pharmaceutical liquid composition according to [3], wherein when the low-molecular-weight polyol includes the first polyol and the second polyol, the content ratios of the first polyol and the second polyol are 10 to 90% by mass and 90 to 10% by mass, respectively, when the total of both is 100% by mass. [5] The liquid pharmaceutical composition according to [1] above, wherein the polyol further comprises a high-molecular-weight polyol having an average molecular weight of more than 300. [6] The liquid pharmaceutical composition according to the above [1], wherein the polyol comprises an amine-based polyol. [7] The pharmaceutical composition according to the above [1], wherein the polyol comprises a polyether polyol having ethylene oxide units and propylene oxide units. [8] A void-filling composition comprising a combination of the chemical composition according to [1] above and a polyisocyanate composition containing a polyisocyanate. [9] A caulking composition comprising the gap filling composition described in [8] above.

[10] A gap filling kit in which the gap filling composition according to [8] above is contained in a multi-chamber container having adjacent first and second chambers, A void filling kit, characterized in that the first compartment contains the chemical liquid composition described in claim 1, and the second compartment contains a polyisocyanate composition containing a polyisocyanate.

[11] The void filling kit according to

[10] , wherein the multi-chamber container is a bag-shaped container having a partition between the first chamber and the second chamber that allows the first chamber and the second chamber to communicate with each other, and when the partition is opened, the chemical solution composition and the polyisocyanate composition are mixed. [Effects of the Invention]

[0008] The void-filling composition of the present invention can be used to form a foam with little shrinkage, no brittleness, and excellent compressive strength. Furthermore, there is sufficient time for the polyol composition (chemical composition) and the polyisocyanate composition to come into contact and initiate the urethane reaction, allowing for rapid curing after foaming. Therefore, when the void-filling composition of the present invention is placed in a void at a civil engineering site, construction site, or the like, a foam with the above properties can be formed. Therefore, the void-filling composition of the present invention can be used as a caulking composition to, for example, provide a waterproofing effect to the void. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram showing an example of a multi-chamber container for accommodating a gap filling composition of the present invention and a method for producing the same. [Figure 2] FIG. 2 is a schematic cross-sectional view showing another example of a multi-chamber container for containing the gap filling composition of the present invention. [Figure 3] FIG. 1 is a schematic explanatory diagram showing a gap filling test in the Examples. [Figure 4] FIG. 1 is a schematic explanatory view showing the formation of a foam in a void filling test in an Example. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below. The matters set forth herein are for illustrative purposes and are intended to exemplify embodiments of the present invention, and are set forth in order to provide what is believed to be the most effective and easily understandable explanation of the principles and conceptual features of the present invention. In this respect, it is not intended to show structural details of the present invention beyond the extent necessary for a fundamental understanding of the present invention, but rather to clarify to those skilled in the art how some aspects of the present invention can be actually embodied.

[0011] The chemical composition of the present invention is a composition containing a polyol and a catalyst, which is used in combination with a polyisocyanate to prepare a void-filling composition. The polyol includes a low-molecular-weight polyol having an average molecular weight of 300 or less, and the content of the low-molecular-weight polyol is 70 mass% or more based on the total amount of the polyol. The catalyst includes an imidazole compound. The "low-molecular-weight polyol" of the present invention can be not only a polyol containing multiple monomer units, but also a compound that does not contain multiple monomer units. Therefore, the term "average molecular weight" refers to, for example, the number-average molecular weight in the former case, and to the molecular weight calculated from the molecular formula in the latter case.

[0012] The polyol according to the present invention is mainly composed of a low-molecular-weight polyol, and the entire amount of the polyol may be a low-molecular-weight polyol. The lower limit of the average molecular weight of the low-molecular-weight polyol is preferably 50, more preferably 70. The polyol may consist solely of a low-molecular-weight polyol, or may consist of a low-molecular-weight polyol and a polyol having an average molecular weight of 300 or less (hereinafter referred to as a "high-molecular-weight polyol"). The low-molecular-weight polyol and the high-molecular-weight polyol may each consist of only one type, or two or more types.

[0013] In the present invention, the low-molecular-weight polyol and the high-molecular-weight polyol do not necessarily differ structurally, such as in the number of hydroxy groups, but merely in average molecular weight. For example, even if the same type of polyol (e.g., polyalkylene glycol) has a plurality of monomer units, the low-molecular-weight polyol and the high-molecular-weight polyol are distinguished only by the difference in average molecular weight. The number of hydroxy groups contained in the low-molecular-weight polyol and the high-molecular-weight polyol may be the same or different, as long as they are two or more.

[0014] In the present invention, the low-molecular-weight polyol and the high-molecular-weight polyol may be a compound selected from a hydrocarbon compound in which at least two hydrogen atoms have been substituted with hydroxy groups, and an organic compound having two or more hydroxy groups and further containing a nitrogen atom, an oxygen atom (excluding oxygen atoms derived from hydroxy groups), a sulfur atom, a phosphorus atom, or a halogen atom (hereinafter referred to as a "polyol component").

[0015] Among the polyol components, examples of compounds consisting of carbon atoms, hydrogen atoms, and oxygen atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, Aliphatic compounds such as glycerol, dipropylene glycol, tripropylene glycol, polyoxypropylene glycol, ditetramethylene glycol, polytetramethylene ether glycol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cycloheptanediol, cyclooctanediol, 1,1-cyclohexanediethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,02,6]decane-dimethanol, and bicyclo[4.Alicyclic compounds such as 3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, 2,2-bis-(4-hydroxycyclohexyl)propane, 1,3-adamantanediol; hydroquinone, resorcinol, dihydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, bisphenol A Examples of the aromatic compounds include diethoxylated bisphenol A, p-xylylene glycol, m-xylylene glycol, o-xylylene glycol, 4,4'-bishydroxymethylbiphenyl, 4,2'-bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, 4,3'-bishydroxymethylbiphenyl, 3,3'-bishydroxymethylbiphenyl, and 3,2'-bishydroxymethylbiphenyl; and further examples include compounds (polyether polyols) obtained by adding at least one alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, and the like to these compounds.

[0016] In the present invention, the polyol component having two or more hydroxyl groups and further containing a nitrogen atom is also preferred, and amine polyols are particularly preferred. Examples of amine polyols include N-alkyl dialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine; trialkanolamines such as triethanolamine and tripropanolamine; compounds obtained by adding alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to these compounds; compounds obtained by adding alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to N,N-dialkyl monoalkanolamines (N,N-dimethylethanolamine, N,N-diethylethanolamine, etc.); compounds obtained by adding alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to compounds having two or more amino groups but not containing hydroxyl groups, such as ethylenediamine-based polyether polyols and tolylenediamine-based polyether polyols.

[0017] Examples of the compound having two or more amino groups and no hydroxy group that is subjected to the alkylene oxide addition include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, and 1,11-undecamethylenediamine. Aliphatic compounds such as amines, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m -Xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenyl)propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene aromatic compounds such as 4,4'-diamino-3,3'-diethyl-5,5-dimethylphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethylbenzidine; and alicyclic compounds such as 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl-dicyclohexylenemethane, 1,4-diaminocyclohexane, and piperazine.

[0018] Both the low-molecular-weight polyol and the high-molecular-weight polyol are preferably aliphatic compounds. When the low-molecular-weight polyol and the high-molecular-weight polyol are alkylene oxide adducts, they are preferably polyol components having ethylene oxide units and propylene oxide units.

[0019] The low-molecular-weight polyol preferably contains a compound represented by the following general formula (1), a compound represented by general formula (2) (polyether polyol), a compound represented by general formula (3), or a compound represented by general formula (4). HO-(R 1 ) n1 -OH (1) HO-(R 2 O) n2 -H (2) [H-(OR 3 ) n3 -O3-R 4 (3) N-(R 5 -OH)3(4) (In the formula, R 1 , R 2 , R 3 and R 5 is a divalent aliphatic hydrocarbon group, and R 4 is a trivalent aliphatic hydrocarbon group, n1 is an integer of 1 to 19, n2 is an integer of 1 to 9, and n3 is an integer of 0 to 3.

[0020] In the above general formulas (1), (2), (3) and (4), R 1 , R 2 , R 3 and R 5 is an aliphatic hydrocarbon group having preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. 1 , R 2 , R 3 and R 5may be one type or two or more types, and in the case of two or more types, they may be two or more types selected from, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2CH2-, etc. Among these, -CH2CH2-, -CH2CH2CH2-, and -CH2CH(CH3)- are preferred.

[0021] In the above general formula (3), R 4 is an aliphatic hydrocarbon group preferably having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.

[0022] In the present invention, one preferred embodiment of the low-molecular-weight polyol is one that contains a polyol component (hereinafter referred to as "first polyol") having an average functionality of 2.5 or more. The average functionality of this first polyol is preferably 2.6 or more, more preferably 2.8 or more, and the upper limit is usually 8. The first polyol preferably contains compounds represented by the above general formulas (3) and (4).

[0023] In the present invention, another preferred embodiment of the low-molecular-weight polyol is one that contains a polyol component having an average functionality of 2 (hereinafter referred to as "second polyol"). The second polyol preferably contains a compound represented by the above general formula (1) or a compound represented by the above general formula (2) (polyether polyol). The compound represented by the above general formula (2) particularly preferably contains ethylene oxide units and propylene oxide units.

[0024] The first polyol and the second polyol can be combined. In this case, the contents of the first polyol and the second polyol, when the total of both is 100% by mass, are preferably 10 to 90% by mass and 90 to 10% by mass, more preferably 25 to 75% by mass and 75 to 25% by mass, and even more preferably 30 to 70% by mass and 70 to 30% by mass, respectively.

[0025] The high molecular weight polyol preferably includes a compound (polyether polyol) represented by the following general formula (5), or an amine-based polyol, which is a compound obtained by adding an alkylene oxide to the above-mentioned compound having no hydroxy group and two or more amino groups. HO-(R 5 O) n4 -H (5) (In the formula, R 5 is a divalent aliphatic hydrocarbon group, and n4 is an integer that results in the molecular weight of the compound exceeding 300.

[0026] The compound represented by the above general formula (5) particularly preferably has an ethylene oxide unit and a propylene oxide unit.

[0027] The compound obtained by adding an alkylene oxide to a compound having two or more amino groups and no hydroxy group is preferably a compound obtained by adding at least one selected from ethylene oxide, propylene oxide, and butylene oxide to ethylenediamine. In the present invention, a compound obtained by adding an alkylene oxide including propylene oxide to ethylenediamine is particularly preferred.

[0028] In the present invention, one preferred embodiment of the high molecular weight polyol used in combination with the low molecular weight polyol is one that contains a polyol component having an average functionality of 2 or more.

[0029] When the polyol according to the present invention is composed of a low-molecular-weight polyol and a high-molecular-weight polyol, the content ratios of the two, when the total content is taken as 100% by mass, are preferably 100 to 70% by mass and 0 to 30% by mass, more preferably 99 to 75% by mass and 1 to 25% by mass, and even more preferably 97 to 85% by mass and 3 to 15% by mass. By using a chemical composition containing a polyol in which the low-molecular-weight polyol and the high-molecular-weight polyol are contained in the above-mentioned ratios and a catalyst containing an imidazole compound, a void-filling composition suitable for forming foams with little shrinkage, no brittleness, and excellent compressive strength can be obtained.

[0030] In order to make the compressive strength of the foam obtained by using the liquid chemical composition of the present invention in combination with a polyisocyanate as a void-filling composition particularly excellent, the liquid chemical composition of the present invention contains an imidazole compound as a catalyst.

[0031] The imidazole compound is a catalyst that promotes urethanization between the polyol contained in the liquid pharmaceutical composition and the polyisocyanate, and examples thereof include 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, etc. The liquid pharmaceutical composition of the present invention may contain only one type of imidazole compound or two or more types of imidazole compounds.

[0032] The content of the imidazole compound contained in the liquid pharmaceutical composition of the present invention is preferably 0.2 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and even more preferably 0.75 to 10 parts by mass, relative to 100 parts by mass of the total amount of polyols.

[0033] The liquid pharmaceutical composition of the present invention may contain a catalyst other than the imidazole compound, if necessary, such as a trimerization catalyst (a catalyst that forms an isocyanurate bond to promote trimerization) for a carboxylate salt, a tertiary ammonium salt, a quaternary ammonium salt, a triazine compound, an aziridine compound, an alcoholate compound, a phenolate compound, or a phenol compound.

[0034] In addition to the above-mentioned essential components, the liquid pharmaceutical composition of the present invention may further contain additives such as a foam stabilizer, a flame retardant, a formaldehyde scavenger, a plasticizer, an antioxidant, an antibacterial agent, a corrosion inhibitor, and a viscosity adjuster.

[0035] The method for producing the liquid pharmaceutical composition of the present invention is not particularly limited. The liquid pharmaceutical composition can be produced by using raw material components in a predetermined ratio and mixing them.

[0036] Next, the gap filling composition of the present invention will be described. The gap filling composition of the present invention is a composition obtained by combining the above-mentioned chemical liquid composition and a polyisocyanate composition containing a polyisocyanate.

[0037] The polyisocyanate composition contains a polyisocyanate, but may also contain a component that does not react with the isocyanate group of the polyisocyanate. The polyisocyanate composition may consist solely of a polyisocyanate.

[0038] Polyisocyanate reacts with polyol in the chemical composition to produce polyurethane (resin), and is a compound having two or more isocyanate groups in the molecule.

[0039] Examples of polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, urethane prepolymers having an isocyanate group at the molecular terminal, isocyanurate-modified polyisocyanates, carbodiimide-modified polyisocyanates, etc. The polyisocyanate composition may contain one type of polyisocyanate or two or more types of polyisocyanates.

[0040] Examples of aromatic polyisocyanates include diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate, dianisidine diisocyanate, isopropylidenebis(cyclohexyl isocyanate), triphenylmethane diisocyanate, triphenylmethane triisocyanate, and dimethyltriphenylmethane tetraisocyanate. Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, and dimer acid diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

[0041] In the present invention, the polyisocyanate preferably includes an aromatic polyisocyanate. The lower limit of the content of the aromatic polyisocyanate relative to the total amount of polyisocyanates constituting the polyisocyanate composition is preferably 70% by mass, more preferably 80% by mass, and even more preferably 90% by mass.

[0042] The polyisocyanate composition may contain other components in addition to the polyisocyanate. Examples of the other components include, among the additives that may be contained in the chemical liquid composition, components that do not react with the polyisocyanate, specifically, foam stabilizers, flame retardants, plasticizers, etc.

[0043] The polyisocyanate contained in the polyisocyanate composition of the present invention reacts with the polyol contained in the chemical liquid composition having the above-mentioned specific configuration to form a polyurethane resin. However, there is sufficient time for the urethane reaction to begin upon contact between the polyol and the polyisocyanate, and the polyisocyanate cures quickly after foaming, providing a foam with little shrinkage, no brittleness, and excellent compressive strength. There is a preferred content ratio between the polyol and the polyisocyanate in the void-filling composition of the present invention. In the present invention, the chemical liquid composition and the polyisocyanate composition are combined so that the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate to the hydroxy groups of the entire polyol component is preferably 0.8 to 3.0, more preferably 1.0 to 2.0.

[0044] By placing the void filling composition of the present invention in voids at civil engineering sites, construction sites, etc., the polyol and polyisocyanate are reacted (cured) to form a foam having excellent compressive strength, which can impart a waterproofing effect, etc. Therefore, the void filling composition of the present invention can be used as a caulking composition.

[0045] When using the gap filling composition of the present invention, the method of supplying the composition is selected depending on the size (volume, etc.) of the gap. Generally, the following methods (H1) and (H2) are used. (H1) A method in which a mixture of a chemical composition and a polyisocyanate composition (a void-filling composition) is prepared in advance and then supplied to the voids. (H2) A method in which the chemical composition and the polyisocyanate composition are supplied separately to the gap so that they meet in the gap.

[0046] However, when the void to be supplied is a part of the space between two or more objects, or is only an opening such as a hole, and the foam does not need to fill the entire space up to the bottom of the hole, for example, the following method (H3), which is an improvement of the above method (H2), can be applied. (H3) A method in which containers containing the liquid chemical composition and the polyisocyanate composition separately are placed in the gap portion, and then the liquid chemical composition and the polyisocyanate composition are made to merge in the container.

[0047] When applying the above method (H3), it is preferable to use a void filling kit (the void filling kit of the present invention) that includes a multi-chamber container with adjacent first and second chambers. The void filling kit of the present invention contains a chemical liquid composition in the first chamber and a polyisocyanate composition containing a polyisocyanate in the second chamber. If the chemical liquid composition and the polyisocyanate composition are contained in the above-mentioned preferred equivalent ratio (NCO / OH), the first and second chambers can be connected and mixed, and then the multi-chamber container can be placed in the gap to form the desired foam.

[0048] The multi-chamber container is preferably a bag-like container that has a partition between the first and second chambers that allows the first and second chambers to communicate with each other, and that allows the chemical solution composition and the polyisocyanate composition to be mixed when the partition is opened.

[0049] FIG. 1(C) is a schematic perspective view showing an example of a multi-chamber container having a partition between the first and second chambers. The multi-chamber container 10X of FIG. 1(C) is constructed by folding the thin-walled cylindrical body 1 made of an elastic material shown in FIG. 1(A) in two as shown in FIG. 2(B), and then folding it vertically as indicated by the arrows in the figure to form the partition 15, thereby forming the first chamber 11 and the second chamber 13. In FIG. 1(C), the outer periphery of the partition 15 is fixed with a partitioning means 17. The liquid chemical composition and the polyisocyanate composition are then poured into the first chamber 11 and the second chamber 13 through the openings at each end, and the chambers are sealed, thereby producing a void filling kit. By opening the partitioning means 17 of the void filling kit and shaking, kneading, handling, etc. the multi-chamber container, the partitioning portion 15 is also opened, and the chemical composition contained in the first chamber 11 and the polyisocyanate composition contained in the second chamber 13 are mixed and foamed and cured.

[0050] The elastic material is not particularly limited and may be a resin, a metal, or a composite material. The elastic material may be one that bursts when the foam is formed.

[0051] Figure 2 is a schematic cross-sectional view showing another example of a multi-chamber container having a partition between the first and second chambers. Multi-chamber container 10Y in Figure 2 has a structure in which first chamber 11 and second chamber 13 are separated by partitions 15a and 15b and a connecting portion 16 that connects them. To facilitate communication between first chamber 11 and second chamber 13 when connecting portion 16 breaks, connecting portion 16 preferably has weak adhesive properties to partitions 15a and 15b. Multi-chamber container 10Y can also be made of the above-mentioned elastic material, but connecting portion 16 can be made of an adhesive or the like.

[0052] Although not shown, an improved version of the multi-chamber container 10Y of FIG. 2 may have a structure in which the connecting portion 16 is not provided and the partition portions 15a and 15b are directly joined together with weak adhesive.

[0053] In the present invention, for example, when a void-filling composition is prepared by mixing a chemical composition and a polyisocyanate composition, both of which are maintained at a substantially constant temperature between 18°C ​​and 23°C, the cream time, which is the time from the start of mixing until foaming begins, can be preferably 15 seconds or more, more preferably 20 to 80 seconds. Furthermore, the gel time, which is the time from the start of mixing of the chemical composition and the polyisocyanate composition until thickening occurs and gel strength begins to develop, can be preferably 25 to 180 seconds, more preferably 30 to 120 seconds. Based on these times, the (cream time / gel time) ratio can be preferably 0.40 to 0.80, more preferably 0.42 to 0.60. This allows sufficient time for the urethanization reaction to begin, allowing for sufficient working time with the void-filling composition of the present invention, and allows for rapid curing after foaming.

[0054] The compressive strength of the foam formed from the ground injection composition of the present invention at 20°C to 25°C is preferably 200 kPa or more, more preferably 400 kPa or more. [Example]

[0055] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" are by mass unless otherwise specified.

[0056] 1. Raw materials for manufacturing medicinal liquid compositions The raw materials for producing the liquid drug composition are shown below.

[0057] 1-1. Polyol 1-1-1. Low molecular weight polyol (1) AGC Dipropylene Glycol (DPG) Molecular weight: 134, Functional groups: 2, Hydroxyl value: 840 mg KOH / g (2) Propylene glycol (PG) manufactured by Tokyo Chemical Industry Co., Ltd. Molecular weight: 76, Functional groups: 2, Hydroxyl value: 1475 mg KOH / g (3) Triethylene glycol (TEG) manufactured by Tokyo Chemical Industry Co., Ltd. Molecular weight: 150, Functional groups: 2, Hydroxyl value: 750 mg KOH / g (4) Sanyo Chemical Industries, Ltd. Polyether polyol "Sannyx GP-250" (product name) Number average molecular weight: 250, Number of functional groups: 3, Hydroxyl value: 670 mg KOH / g (5) Triethanolamine (TEA) manufactured by Tokyo Chemical Industry Co., Ltd. Molecular weight: 149, Functional groups: 3, Hydroxyl value: 1130 mg KOH / g

[0058] 1-1-2. High molecular weight polyol (1) AGC "Exenol 450ED" (product name) Polyether polyol obtained by adding 48% propylene oxide to ethylenediamine Number average molecular weight: 500, Number of functional groups: 4, Hydroxyl value: 450 mg KOH / g (2) Sanyo Chemical Industries, Ltd. Polyether polyol "Sannyx PP-400" (product name) Number average molecular weight: 400, Number of functional groups: 2, Hydroxyl value: 280 mg KOH / g (3) Sanyo Chemical Industries, Ltd. Polyether polyol "Sannyx GP-400" (product name) Number average molecular weight: 400, Number of functional groups: 3, Hydroxyl value: 400 mg KOH / g

[0059] 1-2. Catalyst (1) Kao Corporation "Kao Raiser No. 120" (product name) 1-Isobutyl-2-methylimidazole (2) Kao Corporation "Kao Raiser No. 390" (product name) Dipropylene glycol solution containing 70% 1,2-dimethylimidazole (3) "Toyocat RX-5" (product name) manufactured by Tosoh Corporation Trimethylaminoethylethanolamine

[0060] 1-3. Foaming agents water

[0061] 1-4.Foam stabilizer Modified silicone "Niax silicone L6978" (product name) manufactured by Momentive Performance Materials Japan

[0062] 1-5.Flame retardants Tris(1-chloro-2-propyl)phosphate (TCPP) manufactured by Wanxiang

[0063] 2. Production and evaluation of medicinal liquid compositions and production and evaluation of void-filling compositions Examples 1 to 17 and Comparative Examples 1 to 7 Using the above raw materials, liquid pharmaceutical compositions were prepared according to the formulations shown in Tables 1 and 2, and the viscosity of the compositions was then measured at 25°C using a B-type viscometer according to the method in accordance with JIS K7117-1. Thereafter, a gap filling composition was produced using the liquid chemical composition obtained above and a polymeric MDI "Wannate PM-130" (trade name) manufactured by Wanhua Chemical Co., Ltd. as a polyisocyanate. The gap filling composition was then used to evaluate the following items, and the results are shown in Tables 1 and 2.

[0064] (1) Reaction test The chemical composition and polyisocyanate were adjusted to 20°C by hand foaming, and weighed into a paper cup (volume: 500 mL) in the proportions shown in the table. The mixture was then mixed at high speed using a Primix Homodisper (trade name) mixer to foam and cure, producing a polyurethane foam. During this process, the cream time (CT) and gel time (GT), which are indicators of the reactivity of the polyol and polyisocyanate, were measured. The cream time (CT) is the time from the start of mixing the two compositions to the start of foaming, and the gel time (GT) is the time from the start of mixing the two compositions to the time the foam surface becomes sticky and stringy. Then, CT / GT was calculated as the rate of change between cream time and gel time. A CT / GT ratio in the range of 0.4 to 0.8 is considered acceptable.

[0065] (2) Measurement of dimensional change rate Test pieces measuring 100 mm × 100 mm × 25 mm were cut out from the polyurethane foam obtained in the reaction test, and the cut test pieces were left standing for 24 hours in an atmosphere at 50° C. After leaving the test pieces standing, the thickness of the test pieces (dimensions after leaving the test pieces standing) was measured, and the dimensional change rate (%) was calculated from the thickness of the test pieces before leaving the test pieces standing (dimensions after cutting: 25 mm) according to the following formula. Dimensional change rate (%) = [(dimension after cutting - dimension after leaving) / dimension after cutting] x 100 Next, the shrinkage was evaluated based on the calculated dimensional change rate according to the following criteria. ○: The dimensional change rate is less than 5%, and there is almost no shrinkage. △: The dimensional change rate is 5% or more and less than 10%, and the degree of shrinkage is small. ×: The dimensional change rate is 10% or more, and the degree of shrinkage is significant.

[0066] (3) Brittleness The polyurethane foam obtained in the reaction test was examined for surface brittleness when the foam that formed as the chemical solution reacted raised above the rim of the cup and the raised part was rubbed with a fingernail while pressing slightly downward, and the surface brittleness was visually observed and evaluated according to the following criteria. ×: The surface was significantly damaged. △: The surface was slightly broken. ○: The surface did not crumble at all.

[0067] (4) Compressive strength A test piece measuring 50 mm x 50 mm x 50 mm was cut out from the foamed layer formed on the plywood so that two skin layers were present within it, and the 10% compressive strength of the obtained test piece was measured using a universal testing machine in accordance with JIS K 7220.

[0068] (5) Gap filling test 1(A) made of aluminum laminate film and having a length of 520 mm, a width of 55 mm, and a seal width of 10 mm, was folded at one-quarter of its length, and an elastic ring 17 was fitted around the folded edge to form a liquid-tight seal, thereby forming a first chamber 11 and a second chamber 13. After that, about 47 ml of the liquid chemical composition and about 122 ml of polyisocyanate were filled into the first chamber 11 and the second chamber 13, respectively, to prepare a void filling kit. Next, elastic ring 17 of the void filling kit was removed, and the chemical composition and polyisocyanate were mixed together to form void filling composition 20 in bag 22 made of aluminum laminate film. Immediately, as shown in FIG. 3 , bag 22 containing void filling composition 20 was inserted into the center of a horizontally placed cylindrical VU PVC pipe 24 with a length of 300 mm and a nominal diameter of 65 mm. Foaming and hardening began within PVC pipe 24, so after one hour, as shown in FIG. 4 , PVC pipe 24 was turned upright, and 500 ml of liquid 32 (polypropylene glycol "Sannyx PP-1000" (trade name) manufactured by Sanyo Chemical Industries, Ltd.) with a viscosity of 150 mPa s was poured into PVC pipe 24 containing foam 30 from above. The condition of PVC pipe 24 after one hour was visually observed and evaluated according to the following criteria. ◯: No liquid leaked below the foam 30. △: Liquid seepage is observed at the interface between the foam 30 and the inner periphery of the PVC pipe 24, but this does not impair performance. ×: Liquid leaked below the foam 30.

[0069] [Table 1]

[0070] [Table 2]

[0071] The following can be seen from Tables 1 and 2. Comparative Examples 1 to 6 are examples using a chemical composition in which the content of low-molecular-weight polyol is less than 70 mass% relative to the total amount of polyol, and the resulting foams showed shrinkage and were highly brittle. Comparative Example 7 is an example using a chemical composition containing a catalyst other than an imidazole compound, and the resulting foams had insufficient compressive strength. Furthermore, in all of Comparative Examples 1 to 7, problems arose when the void-filling compositions were used in caulking tubes. On the other hand, in Examples 1 to 17, gap filling compositions with excellent workability into gaps, with CT / GT of 0.40 to 0.80, were obtained, and the polyurethane foams formed had little shrinkage, high compressive strength of 200 kPa or more, and no (low) brittleness, and it was found that the gap filling compositions can be suitably used in caulking tubes. [Industrial Applicability]

[0072] The present invention is suitable for application to voids at civil engineering sites, construction sites, etc., and can form a foam in the void that has little shrinkage, is not brittle, and has excellent compressive strength, so it can impart a waterproofing effect to the void, for example. [Explanation of symbols]

[0073] 10X,10Y: Multi-chamber container 11: Room 1 13: 2nd room 15, 15a, 15b: Partition 16:Joint part 17: Partition means 20: Void filling composition 22: Bag body

Claims

1. A chemical composition used in combination with a polyisocyanate to prepare a void filling composition, comprising: Contains a polyol and a catalyst, the polyol contains a low-molecular-weight polyol having an average molecular weight of 300 or less, and the content of the low-molecular-weight polyol is 70 mass% or more based on the total amount of the polyol; The chemical composition, wherein the catalyst contains an imidazole compound.

2. The chemical liquid composition according to claim 1 , wherein the low-molecular-weight polyol comprises a first polyol having an average functionality of 2.5 or more.

3. The chemical liquid composition according to claim 1 or 2, wherein the low-molecular-weight polyol comprises a second polyol having an average functionality of two.

4. 4. The pharmaceutical composition according to claim 3, wherein when the low-molecular-weight polyol contains the first polyol and the second polyol, the contents of the first polyol and the second polyol are 10 to 90% by mass and 90 to 10% by mass, respectively, when the total of the first polyol and the second polyol is 100% by mass.

5. The pharmaceutical composition according to claim 1 , wherein the polyol further comprises a high-molecular-weight polyol having an average molecular weight of more than 300.

6. The liquid pharmaceutical composition according to claim 1 , wherein the polyol comprises an amine-based polyol.

7. 2. The pharmaceutical composition according to claim 1, wherein the polyol comprises a polyether polyol having ethylene oxide units and propylene oxide units.

8. A void-filling composition comprising a combination of the chemical composition according to claim 1 and a polyisocyanate composition containing a polyisocyanate.

9. A caulking composition comprising the gap filling composition of claim 8.

10. A gap filling kit comprising the gap filling composition according to claim 8 housed in a multi-chamber container having adjacent first and second chambers, A void filling kit, characterized in that the first chamber contains the chemical liquid composition according to claim 1, and the second chamber contains a polyisocyanate composition containing a polyisocyanate.

11. The void filling kit according to claim 10, wherein the multi-chamber container is a bag-shaped container having a partition between the first chamber and the second chamber that allows the first chamber and the second chamber to communicate with each other, and wherein the chemical solution composition and the polyisocyanate composition are mixed when the partition is opened.

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