JP2023147053A - Chemical liquid composition for injection into soil, expanded body and production method of the same - Google Patents

Abstract

To provide a chemical liquid composition which has a preferable foaming ratio, and reduces a reaction temperature dependency for preventing foaming failure, an expanded body and a production method of the same.SOLUTION: There is provided a chemical liquid composition for injection into soil which is formed of: two kinds of liquid which are A liquid and B liquid. The A liquid includes: a water soluble silicate; polyol; and a catalyst. The B liquid includes polyisocyanate, and includes as catalysts, two kinds of tertiary amines which are a first tertiary amine having a hydroxy group and a second tertiary amine having no hydroxy group. The polyol is polyol whose number average molecular weight is greater than 200. An expanded body is obtained by mixing the A liquid and the B liquid forming the chemical liquid composition for injection into soil. A production method of the expanded body forms the expanded body by mixing the A liquid and the B liquid forming the chemical liquid composition for injection into soil.SELECTED DRAWING: None

Description

The present invention relates to a chemical composition for ground injection, a foam, and a method for producing the same. More specifically, the present invention relates to a chemical composition for ground injection using a silicate and a polyisocyanurate, a foam, and a method for producing the same.

Foamed urethane grout has conventionally been known as a grout material used for ground improvement, filling cavities in structures, and the like. Since foamed urethane grout as a reaction product is essentially an organic material obtained by reacting a polyol and a polyisocyanate, it is necessary to incorporate a flame retardant in order to obtain high flame retardancy. Further, foamed urethane grout has a problem in that its raw material cost is high.
On the other hand, a composite grout obtained as a composite reaction product of an inorganic material and an organic material is known, in which a part of the polyol is replaced with water glass (silicate aqueous solution), which is an inorganic material. Composite grout contains an inorganic material in the aggregate, so it has superior flame retardancy compared to grout made only of organic aggregate. Composite grouts also have the advantage of low raw material costs. Techniques regarding such composite grouts are known from Patent Documents 1 and 2 listed below.

Japanese Patent Application Publication No. 2001-152154 JP2011-037946A

Patent Document 1 discloses that by forming a foamed inorganic-organic composite solid, rock or ground and artificial materials with high consolidation strength, stable reinforcement effect, durability, pouring workability, and economical efficiency can be obtained. For the purpose of stabilizing the structure or making it watertight (Patent Document 1 [0007]), (A) an aqueous alkali silicate solution, (B) an organic polyisocyanate composition, and (C) a molecular weight of less than 120. An injection chemical composition for stabilizing the ground, artificial structures, etc. (Patent Document 1 [Claim 1]) comprising an imidazole catalyst and (D) an aliphatic tertiary amine catalyst having a molecular weight of less than 120 is disclosed. ing.

Patent Document 2 discloses that it suppresses separation of a silicate aqueous solution, has excellent compatibility between the silicate aqueous solution and an isocyanate component, suppresses elution of organic compounds from a cured product, and prevents environmental pollution (especially water pollution). The aim of the present invention is to provide a composition for rock bolt fixing material, which can suppress the damage, impart high strength to the cured product, and have excellent long-term durability (Patent Document 2 [0010]). A composition for a rock bolt fixing material to be cast in surrounding ground, the fixing material composition comprising a component (A) containing an aqueous silicate solution and a component (B) containing an isocyanate compound, The (A) component contains (A1) an aqueous sodium silicate solution, and (A2) an amine polyol selected from the group consisting of trialkanolamine and alkyl dialkanolamine, and the (B) component contains (B1) A composition for a rock bolt fixing material (Patent Document 2 [Claim 1]) is disclosed, which contains an isocyanate compound and (B2) an ester compound consisting of an aliphatic alcohol having 8 to 12 carbon atoms and a polybasic acid. .

In these grout materials, while the foaming ratio can be controlled by selecting a catalyst, the selection of the catalyst may result in temperature-sensitive properties. In particular, when the reaction environment becomes high temperature, foaming becomes unstable, and for example, shrinkage may occur after foaming, cavities may be formed in the foam, and foam cells may become non-uniform. It is preferable to avoid such foaming defects as they affect the strength of the resulting composite grout, but as mentioned above, it is possible to reduce temperature dependence and prevent foaming defects while ensuring a good foaming ratio. It's not easy.

The present invention has been made in view of the above-mentioned circumstances, and provides a chemical composition for ground injection, a foam, and the like, which can reduce reaction temperature dependence and prevent foaming defects while having a good foaming ratio. The purpose is to provide a manufacturing method.

That is, the present invention is as shown below.
[1] A chemical liquid composition for ground injection consisting of two types of chemical liquids, liquid A and liquid B,
The liquid A contains a water-soluble silicate, a polyol, and a catalyst,
The B liquid contains polyisocyanate,
The catalyst includes two types of tertiary amines, a first tertiary amine having a hydroxy group and a second tertiary amine not having a hydroxy group,
A chemical composition for ground injection, wherein the polyol is a polyol having a number average molecular weight of more than 200.
[2] The chemical composition for ground injection according to [1] above, wherein the polyol is a polyether polyol.
[3] The chemical liquid for ground injection according to [2] above, wherein the polyether polyol includes a polyether polyol having a number average molecular weight of more than 200 and less than 500, and a polyether polyol having a number average molecular weight of 500 or more. Composition.
[4] The chemical composition for ground injection according to any one of [1] to [3] above, wherein the polyol is 8% by mass or less based on 100% by mass of the entire liquid A.
[5] The first tertiary amine is the base according to any one of [1] to [4] above, which does not have a ring structure in the main chain that includes a tertiary amino group and the hydroxy group. Pharmaceutical liquid composition for injection.
[6] The first tertiary amine has an oxygen atom and/or a nitrogen atom in the main chain that includes a tertiary amino group and the hydroxyl group. The chemical composition for ground injection described above.
[7] The chemical composition for ground injection according to any one of [1] to [6] above, wherein the first tertiary amine has a dimethylamino group.
[8] The chemical composition for ground injection according to any one of [1] to [7] above, wherein the second tertiary amine does not have a ring structure.
[9] A foam obtained by mixing the liquid A and the liquid B constituting the chemical composition for ground injection according to any one of [1] to [8] above.
[10] A foam is formed by mixing the liquid A and the liquid B constituting the chemical composition for ground injection according to any one of [1] to [8] above. Method of manufacturing foam.

According to the chemical composition for ground injection of the present invention, it is possible to obtain a foam that has a good expansion ratio while reducing reaction temperature dependence and preventing foaming defects.
According to the foam of the present invention, poor foaming can be prevented.
According to the method for producing a foam of the present invention, it is possible to obtain a foam that has a good expansion ratio and is prevented from foaming defects.

The present invention will be described below based on specific embodiments. However, the present invention is not limited to these embodiments. These embodiments are merely examples for convenience of explanation, and the present invention is not limited thereto in any way, and the present invention can be modified in various ways depending on the purpose and use. Additionally, all publications, patents, and patent applications cited herein are incorporated by reference in their entirety.
Further, in this specification, the description "XX to YY" means "XX or more and YY or less". Furthermore, for the compounds exemplified in this specification, the CAS registration number may be written together with some of the compound names that have multiple notation methods, but since the CAS registration number differs depending on the isomer form, etc., the compound names listed together may be This represents one example of the above, and there is not a one-to-one correspondence between compound names and CAS registration numbers.

[1] Liquid chemical composition for ground injection The liquid chemical composition for ground injection of the present invention (hereinafter also simply referred to as "this composition") is composed of two types of chemical liquids, liquid A and liquid B,
Liquid A contains a water-soluble silicate, a polyol, and a catalyst,
Liquid B contains polyisocyanate,
As a catalyst, a first tertiary amine having a hydroxyl group (hereinafter also referred to as "primary-tertiary amine") and a second tertiary amine not having a hydroxyl group (hereinafter also referred to as "secondary-tertiary amine") are used. ) and two types of tertiary amines,
The polyol is characterized in that it has a number average molecular weight of more than 200.

[1] Liquid A Liquid A contains a "water-soluble silicate," a "polyol," and a "catalyst."

(1) Water-soluble silicate Water-soluble silicate is a silicate compound exhibiting water solubility, and includes what is generally called water glass. Metasilicates, orthosilicates, etc. can also be used if they exhibit water solubility.
The types of cations constituting the water-soluble silicate are not limited, but include monovalent alkali metal ions (Li ions, Na ions, K ions, etc.), ammonium ions, and the like. That is, examples of water-soluble silicates include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, and the like. These may be used alone or in combination of two or more. In the present invention, among the above, sodium silicate (sodium silicate) is preferred because it is inexpensive and easily available.

Sodium silicate can generally be expressed as Na ₂ O.nSiO ₂ , of which n>1 in water-soluble sodium silicate, and n in water-soluble sodium silicate used in the present invention is 2. .0 to 4.0 is preferable. Within this range, not only is storage stability excellent, but also low-temperature coagulation can be suppressed.
Moreover, when preparing Liquid A, a water-soluble silicate is usually blended as an aqueous solution thereof (hereinafter also simply referred to as "silicate aqueous solution"). The silicate aqueous solution may be prepared and used as appropriate, but since it is also commercially available as a silicate aqueous solution (sodium silicate aqueous solution), sodium silicate, water glass, etc., these commercial products can be used. Regarding sodium silicate, each sodium silicate such as No. 1, No. 2, No. 3, etc. specified in the JIS standard (JIS K1408) can be used. These may be used alone or in combination of two or more. Further, it is possible to use, for example, No. 4, No. 5, etc., No. 1.5, No. 2.5, etc., which are formulated in accordance with this JIS standard. These may be used alone or in combination of two or more.
The solid content of the silicate aqueous solution is not limited, but from the viewpoint of stability and solidification properties of liquid A, it is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, based on the entire silicate aqueous solution. .

The amount of water-soluble silicate contained in liquid A is not limited, but when the entire liquid A is 100% by mass, it is preferable that the total of water-soluble silicate and water is 80% by mass or more, It is more preferably 85% by mass or more, even more preferably 88% by mass or more, and particularly preferably 89% by mass or more. On the other hand, this content is usually 99.99% by mass or less, more preferably 99.8% by mass or less, even more preferably 99.6% by mass or less, and particularly preferably 99.4% by mass or less. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be 80 to 99.99% by mass, it can be 85 to 99.8% by mass, it can be 88 to 99.6% by mass, and it can be 89 to 99.4% by mass. It can be done. Note that the above-mentioned water means the total amount of water contained in the A liquid. That is, water at this time is the amount of water contained in the aqueous solution when water-soluble silicate is used as an aqueous solution (i.e., water glass), the amount of water contained in other additives, and the amount of water contained in the aqueous solution. It is the sum of what has been added.

(2) Polyol Polyol is an organic compound having two or more hydroxy groups. The type of polyol is not limited, and any polyol that has conventionally been used as a component of a chemical composition for ground injection can be used as appropriate. That is, examples of polyols include aliphatic polyols, polyester polyols, polyether polyols, polycarbonate polyols, olefin polyols, acrylic polyols, and siloxane polyols. Among these, aliphatic polyols, polyester polyols, and polyether polyols are preferred, and polyether polyols are particularly preferred. These may be used alone or in combination of two or more.

Aliphatic polyols include those with two hydroxy groups such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, dialkylpropanediol, tetramethylene diol, hexamethylene diol, nonane diol, and methyloctanediol. Compounds having three or more hydroxy groups such as glycerin, trimethylolpropane and trimethylolethane; Sugar alcohols such as xylitol and sorbitol. These may be used alone or in combination of two or more.

Examples of polyester polyols include condensation polymers of aliphatic polyols and polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reaction products of three types of components: aliphatic polyols, polycarboxylic acids, and cyclic esters. can be mentioned. These may be used alone or in combination of two or more.
Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid. Examples include aromatic dicarboxylic acids such as alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid, and trimellitic acid. Examples of the cyclic ester include propiolactone, valerolactone, caprolactone, and the like. These may be used alone or in combination of two or more.

The polyether polyol includes (1) a reaction product obtained by addition reaction with an alkylene oxide using a compound having 2 or more active hydrogens as an initiator, and (2) a reaction product obtained by reacting phenols, aldehydes, and secondary amines. Mannich condensates, (3) Mannich polyether polyols prepared by adding alkylene oxide to the Mannich condensates, and the like. These may be used alone or in combination of two or more.
In addition, examples of the compound having two or more active hydrogens in (1) above include polyhydric alcohols, amine compounds, and the like. These may be used alone or in combination of two or more. Among these, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, butylene glycol, pentamethylene glycol, hexamethylene glycol, butanediol, glycerin, trimethylolpropane, pentaerythritol, and the like. These may be used alone or in combination of two or more. Examples of the amine compound include diamines such as ethylenediamine, toluenediamine, and tolylenediamine; alkanolamines such as ethanolamine and diethanolamine. These may be used alone or in combination of two or more. Further, examples of the alkylene oxide include ethylene oxide and propylene oxide. These may be used alone or in combination of two or more.

Among the various polyols mentioned above, the present composition preferably contains a polyether polyol. When using a polyether polyol, the silicate aqueous solution and isocyanate have better miscibility than when using other polyols, and chemical stability can be improved.

Further, when using a polyether polyol, its molecular weight is not limited, but it is preferably a number average molecular weight of more than 200. When a polyether polyol with a number average molecular weight of over 200 is used, foaming stability is higher than when a number average molecular weight of 200 or less is used, reducing the influence of foaming temperature, and improving high temperature foaming. stability can be improved. That is, it is possible to suppress the rate at which the expansion ratio changes depending on the foaming temperature, and it is also possible to suppress shrinkage, cavitation, and coarsening of the foam obtained when the foaming temperature is high. The number average molecular weight of the polyether polyol is more preferably 250 or more, even more preferably 300 or more, and particularly preferably 350 or more. On the other hand, the number average molecular weight of the polyether polyol is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, and particularly preferably 2,500 or less. These upper and lower limit values can be arbitrarily combined. That is, for example, when the number average molecular weight of the polyether polyol is Mn, Mn can be 200<Mn≦10000, 250<Mn≦7000, and 300<Mn≦5000. 350<Mn≦2500.
The number average molecular weight of the polyether polyol can be measured according to JIS K7252-2 or calculated from the hydroxyl value.

In the present composition, it is further preferable to use two or more polyether polyols having different Mn values (Mn>200) in combination. By using this combination, the stability of high temperature foaming can be further improved and the foaming ratio can be further stabilized. That is, it is possible to more effectively suppress shrinkage, cavitation, and coarsening of the foam obtained when the foaming temperature is high, and to prevent the expansion ratio from becoming relatively large or relatively small.

When polyether polyols with different Mn values are used together, any number of polyether polyols with different Mn values may be used together, but from the viewpoint of cost and production, 2 to 3 types are preferred, and 2 types are particularly preferred. When two types of polyether polyols with different Mn are used together, a polyether polyol with a smaller Mn is used as the first polyether polyol, Mn of the first polyether polyol is set as "Mn1", and a polyether with a larger Mn is used. When the polyol is a second polyether polyol and the Mn of the second polyether polyol is "Mn2", 200<Mn1 and 200<Mn2.

Preferably, Mn1 and Mn2 differ by at least 100 (100≦Mn2−Mn1), and more preferably by at least 200 (200≦Mn2−Mn1). The difference in Mn (Mn2-Mn1) is usually 2500 or less (Mn2-Mn1≦2500), preferably 800 or less (Mn2-Mn1≦800), and more preferably 500 or less (Mn2-Mn1≦500). That is, for example, 100≦Mn2-Mn1≦2500, 200≦Mn2-Mn1≦800, and 200≦Mn2-Mn1≦500.
That is, for example, 200<Mn1≦500, 500<Mn2≦5000 and 100≦Mn2-Mn1, and 300≦Mn1≦500, 500<Mn2≦2500 and 200≦Mn2-Mn1. be able to

Furthermore, when polyol is included in liquid A, its content is not limited, but when the total amount of water-soluble silicate and water contained in liquid A is 100 parts by weight, the polyol may be 20 parts by weight or less. It is preferable that there be. When the polyol content is 20 parts by mass or less, the generation of foam in flowing water can be suppressed and the defoaming time can be shortened, and costs can be reduced, compared to when the polyol content is more than 20 parts by mass. can do. The content of the polyol is more preferably 15 parts by mass or less, still more preferably 13 parts by mass or less, and particularly preferably 12 parts by mass or less. On the other hand, the content of polyol is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 1.5 parts by mass or more. These upper and lower limit values can be arbitrarily combined. That is, for example, the content of the polyol can be 0.1 to 20 parts by mass, and 0.5 to 15 parts by mass, when the water-soluble silicate contained in liquid A is 100 parts by mass. The amount can be 1 to 13 parts by mass, and can be 1.5 to 12 parts by mass. In addition, in order to suppress the generation of bubbles in flowing water and shorten the defoaming time, the polyol is preferably 8% by mass or less, more preferably 7% by mass or less, and 6% by mass, based on 100% by mass of the entire liquid A. The following are more preferred.

(3) Catalyst The catalyst serves as a catalyst when forming a foam (foamed solidified body), which is a reaction product, from the components contained in Liquids A and B after mixing Liquids A and B. It is an ingredient. The present composition contains two types of tertiary amines as the catalyst: "primary-tertiary amine" and "secondary-tertiary amine."

(3-1) Primary-tertiary amine Primary-tertiary amine is a tertiary amine having a hydroxy group.
When primary-tertiary amines are used alone, the problem of poor foaming stability arises, but in this composition, when used in combination with secondary-tertiary amines, the catalyst as a whole functions effectively. Ru. Specifically, it is considered that the combined use of primary and tertiary amines has the effect of reducing the temperature dependence of the reaction and the effect of suppressing foaming failure. In addition, since primary to tertiary amines have hydroxy groups, their affinity for water-soluble silicates is improved compared to tertiary amines that do not have hydroxy groups, and the affinity between water-soluble silicates and polyisocyanates is improved. It is thought that it can promote the reaction. In this way, it is thought that by using a primary-tertiary amine and a secondary-tertiary amine in combination, it is possible to reduce reaction temperature dependence and prevent foaming defects while ensuring a good expansion ratio for the catalyst as a whole.

The primary-tertiary amine may have only one tertiary amino group, or may have two or more. Further, it may have only one hydroxy group or two or more hydroxy groups. Therefore, examples of primary to tertiary amines include (1) compounds having one tertiary amino group and one hydroxy group. Further, (2) a compound having a plurality of tertiary amino groups and one hydroxy group may be mentioned. Further examples include (3) a compound having one tertiary amino group and a plurality of hydroxy groups. These may be used alone or in combination of two or more.

The above (1) primary-tertiary amines having one tertiary amino group and one hydroxy group include 2-(dimethylamino)ethanol (CAS RN: 108-01-0), 2-(ethylmethyl amino) ethanol (CAS RN: 2893-43-8), 2-(diethylamino) ethanol (CAS RN: 100-37-8), 3-(dimethylamino)-1-propanol (CAS RN: 3179-63-3) ), 1-(dimethylamino)-2-propanol (CAS RN: 108-16-7), 2-[ethyl(methyl)amino]-1-propanol (CAS RN: 1060817-16-4), 3-( diethylamino)-1-propanol (CAS RN: 622-93-5), 1-(diethylamino)-2-propanol (CAS RN: 4402-32-8), 4-(dimethylamino)-1-butanol (CAS RN :13330-96-6), 3-(dimethylamino)-1-butanol (CAS RN:2893-65-4), 4-(diethylamino)-1-butanol (CAS RN:2683-56-9), 6 -(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 2-[2-(diethylamino) ) ethoxy]ethanol (CAS RN: 140-82-9), 4-(dimethylamino)benzyl alcohol (CAS RN: 1703-46-4), 2-[4-(dimethylamino)phenyl]ethanol (CAS RN: 50438-75-0), 1-methyl-4-piperidine methanol (CAS RN: 20691-89-8), 1-methyl-3-piperidine methanol (CAS RN: 7583-53-1), 1-methyl-2 -Piperidine methanol (CAS RN: 20845-34-5) and the like. These may be used alone or in combination of two or more. Among these, primary-tertiary amines having a tertiary amino group having a methyl group directly connected to a nitrogen atom (hereinafter also simply referred to as "methyl tertiary amino group") are preferred as the tertiary amino group. More preferred are primary-tertiary amines having a tertiary amino group (hereinafter also simply referred to as "dimethyl tertiary amino group") having two methyl groups directly connected to a nitrogen atom.

The above (2) primary-tertiary amine having multiple tertiary amino groups and one hydroxy group is 1,3-bis(dimethylamino)-2-propanol (CAS RN:5966-51-8 ), 1,3-bis(diethylamino)-2-propanol (CAS RN: 3492-47-5), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0 ), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7), 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN: 90 -72-2), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (CAS RN:83016-70-0), and the like. These may be used alone or in combination of two or more. Among these, as the tertiary amino group, primary-tertiary amines having a methyl tertiary amino group are preferred, and primary-tertiary amines having a dimethyl tertiary amino group are more preferred.

The above (3) primary-tertiary amine having one tertiary amino group and multiple hydroxy groups includes 3-(dimethylamino)-1,2-propanediol (CAS RN: 623-57-4 ), 3-(diethylamino)-1,2-propanediol (CAS RN: 621-56-7), N-methyldiethanolamine (CAS RN: 105-59-9), N-ethyldiethanolamine (CAS RN: 139- Examples include compounds having one methyl tertiary amino group and multiple hydroxy groups such as 87-7). These may be used alone or in combination of two or more.

Among the above, 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62 -7), 2-[2-(diethylamino)ethoxy]ethanol (CAS RN: 140-82-9), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) ) ether (CAS RN:83016-70-0). Compared to primary to tertiary amines that do not have oxygen atoms in their main chains, these amines have a further improved affinity for water-soluble silicates, and the reaction between water-soluble silicates and polyisocyanates is enhanced. Since it is considered to promote amines, it is more preferable as a primary-tertiary amine. These may be used alone or in combination of two or more.

Among the above, 2-[[2-(dimethylamino)ethyl]methylamino]ethanol ( CAS RN:2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN:67151-63-7), N,N,N'-trimethyl-n '-(2-hydroxyethyl)bis(2-aminoethyl)ether (CAS RN:83016-70-0). Compared to primary to tertiary amines that do not have nitrogen atoms in their main chains, these have a further improved affinity for water-soluble silicates, and the reaction between water-soluble silicates and polyisocyanates is enhanced. Since it is considered to promote amines, it is more preferable as a primary-tertiary amine. These may be used alone or in combination of two or more.

In addition, among the above, as primary-tertiary amines whose tertiary amino group is a dimethylamino group (dimethyl tertiary amino group), 2-(dimethylamino)ethanol (CAS RN: 108-01-0), 3-(dimethylamino)-1-propanol (CAS RN: 3179-63-3), 1-(dimethylamino)-2-propanol (CAS RN: 108-16-7), 4-(dimethylamino)-1 -Butanol (CAS RN: 13330-96-6), 3-(dimethylamino)-1-butanol (CAS RN: 2893-65-4), 6-(dimethylamino)-1-hexanol (CAS RN: 1862- 07-3), 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 4-(dimethylamino)benzyl alcohol (CAS RN: 1703-46-4), 2-[ 4-(dimethylamino)phenyl]ethanol (CAS RN:50438-75-0), 1,3-bis(dimethylamino)-2-propanol (CAS RN:5966-51-8), 2-[[2- (dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol (CAS RN: 67151-63-7) , 2,4,6-tris(dimethylaminomethyl)phenol (CAS RN:90-72-2), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl) Examples include ether (CAS RN: 83016-70-0), 3-(dimethylamino)-1,2-propanediol (CAS RN: 623-57-4). By having a dimethyl tertiary amino group, the tertiary amino group constitutes the terminal end of the compound. Furthermore, since the number of carbon atoms in the hydrocarbon group constituting the tertiary amino group is small, the steric hindrance of the terminal tertiary amino group can be reduced, which further improves the catalytic activity at the initial stage of the reaction of primary-tertiary amines. It is thought that it is possible to do so.

Moreover, among the above, as a primary-tertiary amine having a dimethyl tertiary amino group and further having an oxygen atom and/or a nitrogen atom in the main chain having a dimethyl tertiary amino group and a hydroxy group, 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), N,N,N'-trimethyl-n'-(2-hydroxyethyl)bis(2-aminoethyl)ether (CAS RN:83016-70-0) is mentioned. These have both the effect of having the dimethyl tertiary amino group mentioned above and the effect of having an oxygen atom and/or nitrogen atom in the main chain that includes a tertiary amino group and a hydroxyl group. It is particularly preferable from the viewpoint that it can have.

(3-2) Secondary-tertiary amine Secondary-tertiary amine is a tertiary amine that does not have a hydroxy group.
When secondary to tertiary amines are used alone, problems arise such as poor foaming stability and temperature dependence of the reaction, but in this composition, primary to tertiary amines When used in combination with an amine, the catalyst as a whole functions effectively. Specifically, it is considered that the combined use of secondary and tertiary amines has the effect of accelerating the overall reaction. On the other hand, since secondary-tertiary amines do not have hydroxyl groups, they are thought to be able to accelerate the reaction of polyisocyanate. In this way, it is thought that by using a primary-tertiary amine and a secondary-tertiary amine in combination, it is possible to reduce the reaction temperature dependence and prevent foaming defects while ensuring an easy-to-handle reaction schedule for the catalyst as a whole.

The secondary-tertiary amine may have only one tertiary amino group or may have two or more. Therefore, examples of secondary-tertiary amines include (1) tertiary amines having only one tertiary amino group. Further, (2) tertiary amines having only two tertiary amino groups can be mentioned. Furthermore, (3) tertiary amines having only three tertiary amino groups can be mentioned. Further, (4) tertiary amines having four or more tertiary amino groups can be mentioned. These may be used alone or in combination of two or more.

The above (1) secondary-tertiary amines having only one tertiary amino group include N,N-dimethylbutylamine (CAS RN:927-62-8) and N,N-diethylbutylamine (CAS RN:4444). -68-2), N,N-dimethylhexylamine (CAS RN:4385-04-0), N,N-dimethyloctylamine (CAS RN:7378-99-6), N,N-dimethyldecylamine ( CAS RN: 1120-24-7), N,N-dimethyldodecylamine (CAS RN: 112-18-5), N,N-dimethylhexadecylamine (CAS RN: 112-69-6), etc. N-Dialkyl-alkylamines, 2-(dimethylamino)ethylamine (CAS RN: 108-00-9), 2-(diethylamino)ethylamine (CAS RN: 100-36-7), 3-(dimethylamino)propyl (Dialkylamino)alkylamines such as amine (CAS RN: 109-55-7), 3-(diethylamino)propylamine (CAS RN: 104-78-9), triethylenediamine (CAS RN: 280-57-9) ), (dimethylamino)acetonitrile (CAS RN: 926-64-7), N,N,N'-trimethylethylenediamine (CAS RN: 142-25-6), trimethylamine (CAS RN: 75-50-3), Triethylamine (CAS RN: 121-44-8), N,N-dimethylcyclohexylamine (CAS RN: 98-94-2), N,N-diethylcyclohexylamine (CAS RN: 91-65-6), 1, 2-dimethylimidazole (CAS RN: 1739-84-0), 1-(dimethylamino)pyrrole (CAS RN: 78307-76-3), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine ( CAS RN:4271-96-9), 4-dimethylaminotoluene (CAS RN:99-97-8), dimethylaniline (CAS RN:121-69-7), 4-dimethylaminoaniline (CAS RN:99- 98-9), 2-(dimethylamino)pyridine (CAS RN: 5683-33-0), 4-(dimethylamino)pyridine (CAS RN: 1122-58-3), 4-(dimethylamino)benzonitrile ( CAS RN: 1197-19-9), N,N-dimethylbenzylamine (CAS RN: 103-83-3), and the like. These may be used alone or in combination of two or more. Among these, secondary-tertiary amines having a tertiary amino group having a methyl group directly connected to a nitrogen atom (hereinafter also simply referred to as "methyl tertiary amino group") are preferred as the tertiary amino group. More preferred are secondary-tertiary amines having a tertiary amino group (hereinafter also simply referred to as "dimethyl tertiary amino group") having two methyl groups directly connected to a nitrogen atom.

The above (2) secondary-tertiary amines having only two tertiary amino groups include N,N,N',N'-tetramethyldiaminomethane (CAS RN:51-80-9), N,N , N',N'-tetramethylethylenediamine (CAS RN:110-18-9), N,N,N',N'-tetraethylethane-1,2-diamine (CAS RN:150-77-6), N,N,N',N'-tetramethyl-1,4-butanediamine (CAS RN:111-51-3), N,N,N',N'-tetramethyl-1,6-hexanediamine ( CAS RN: 111-18-2) and other tetraalkylalkane diamines, bis(2-(N,N-dimethylamino)ethyl) ether (CAS RN: 3033-62-3), tert-butoxybis(dimethylamino) Methane (CAS RN:5815-08-7), 4,4'-bis-(dimethylamino)benzophenone (CAS RN:90-94-8), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN:6711-48-4), N,N,N',N'-tetramethyl-1,3-diaminobutane (CAS RN:97-84-7), N,N'-dimethylpiperazine (CAS RN:106-58-1), N,N,N',N'-tetramethyl-1,8-naphthalenediamine (CAS RN:20734-58-1), 4-methylmorpholine (CAS RN:109-02) -4) etc. These may be used alone or in combination of two or more. Among these, as the tertiary amino group, secondary-tertiary amines having a methyl tertiary amino group are preferred, and secondary-tertiary amines having a dimethyl tertiary amino group are more preferred.

The above (3) secondary-tertiary amines having only three tertiary amino groups include 1-(2-dimethylaminoethyl)-4-methylpiperazine (CAS RN: 104-19-8), N,N , N', N'', N''-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), tris(dimethylamino)methane (CAS RN: 5762-56-1), bis(4-dimethylaminophenyl) )-4-dimethylamino-d6-phenylmethane (CAS RN: 1173023-92-1) and the like. These may be used alone or in combination of two or more. Among these, as the tertiary amino group, secondary-tertiary amines having a methyl tertiary amino group are preferred, and secondary-tertiary amines having a dimethyl tertiary amino group are more preferred.

The above (4) secondary-tertiary amines having four or more tertiary amino groups include tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), tetrakis(dimethylamino)ethylene (CAS RN: 996-70-3), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS RN: 3083-10-1), and the like. These may be used alone or in combination of two or more. Among these, as the tertiary amino group, secondary-tertiary amines having a methyl tertiary amino group are preferred, and secondary-tertiary amines having a dimethyl tertiary amino group are more preferred.

Furthermore, among the above, the secondary-tertiary amine is preferably a compound having a plurality of tertiary amino groups. Therefore, as mentioned above, (2) tertiary amine having only two tertiary amino groups, (3) tertiary amine having only three tertiary amino groups, and (4) tertiary amine having four or more tertiary amino groups. Preferably, it is at least one of amines.
Furthermore, the tertiary amino group of the secondary-tertiary amine in the present composition is preferably a dimethylamino group (ie, a dimethyl tertiary amino group). By having a dimethylamino group, a tertiary amino group constitutes the terminal end of the compound. Furthermore, since the number of carbon atoms in the hydrocarbon group constituting the tertiary amino group is small, the steric hindrance of the terminal tertiary amino group can be reduced, which further improves the catalytic activity at the initial stage of the reaction of secondary-tertiary amines. It is thought that it is possible to do so.
Therefore, the secondary-tertiary amine in the present composition has a plurality of tertiary amino groups, and at least two of the tertiary amino groups are dimethylamino groups (i.e., dimethyl tertiary amino groups). ) is more preferable. In addition, the secondary-tertiary amine in the present composition preferably does not have a ring structure in the main chain connecting different tertiary amino groups.

As mentioned above, as secondary-tertiary amines that have multiple dimethylamino groups and do not have a ring structure in the main chain connecting the dimethylamino groups, N,N,N',N'-tetra Methyldiaminomethane (CAS RN:51-80-9), N,N,N',N'-tetramethylethylenediamine (CAS RN:110-18-9), N,N,N',N'-tetramethyl -1,4-butanediamine (CAS RN:111-51-3), N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN:111-18-2), etc. Alkyl alkanediamines, bis(2-(N,N-dimethylamino)ethyl)ether (CAS RN: 3033-62-3), tert-butoxybis(dimethylamino)methane (CAS RN: 5815-08-7), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN:6711-48-4), N,N,N',N'-tetramethyl-1,3-diaminobutane (CAS RN:97 -84-7), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS RN:3030-47-5), tris(dimethylamino)methane (CAS RN:5762-56-1) ), tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), tetrakis(dimethylamino)ethylene (CAS RN: 996-70-3), 1,1,4,7,10 ,10-hexamethyltriethylenetetramine (CAS RN:3083-10-1)

Further, as the secondary to tertiary amine in the present composition, a compound having an oxygen atom and/or a nitrogen atom in the main chain connecting different tertiary amino groups can be suitably used.
That is, compounds having a plurality of dimethylamino groups, no ring structure in the main chain connecting the dimethylamino groups, and an oxygen atom and/or nitrogen atom in the main chain connecting the dimethylamino groups are preferred. Available for Such secondary-tertiary amines include bis(2-(N,N-dimethylamino)ethyl)ether (CAS RN: 3033-62-3), tert-butoxybis(dimethylamino)methane (CAS RN: 5815-08-7), 3,3'-iminobis(N,N-dimethylpropylamine) (CAS RN:6711-48-4), N,N,N',N'',N''-pentamethyl Diethylenetriamine (CAS RN: 3030-47-5), Tris[2-(dimethylamino)ethyl]amine (CAS RN: 33527-91-2), 1,1,4,7,10,10-hexamethyltriethylene Examples include tetramine (CAS RN: 3083-10-1). These may be used alone or in combination of two or more.

(3-3) Amount of catalyst The amount of catalyst contained in liquid A (total amount of primary-tertiary amine and secondary-tertiary amine) is not limited, but 100 mass of polyisocyanate contained in liquid B is not limited. The amount is preferably 0.05 parts by mass or more, can be 0.1 parts by mass or more, can be 0.3 parts by mass or more, and can be 0.5 parts by mass or more. The amount can be 0.7 parts by mass or more. On the other hand, this content is preferably 5 parts by mass or less, can be 4 parts by mass or less, can be 3 parts by mass or less, can be 2 parts by mass or less, and can be 1.6 parts by mass or less. It can be less than or equal to parts by mass. These upper and lower limit values can be arbitrarily combined. That is, for example, it is preferably 0.05 to 5 parts by mass, can be 0.1 to 4 parts by mass, can be 0.3 to 3 parts by mass, and can be 0.5 to 2 parts by mass. The amount can be 0.7 to 1.6 parts by mass. In a preferable range, it is possible to reduce reaction temperature dependence and prevent foaming defects while developing a good foaming ratio.

In addition, although the quantitative ratio of primary-tertiary amine and secondary-tertiary amine is not limited, when the total of primary-tertiary amine and secondary-tertiary amine is 100% by mass, The proportion of primary-tertiary amine is preferably 5% by mass or more, can be 10% by mass or more, and can be 18% by mass or more. On the other hand, this proportion is preferably 95% by mass or less, can be 85% by mass or less, and can be 75% by mass or less. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be 5 to 95% by weight, 10 to 85% by weight, and 18 to 75% by weight.

(3-4) Other Catalysts In addition, other catalysts than the above-mentioned primary-tertiary amines and secondary-tertiary amines can be blended in the A liquid. However, the amount of other catalysts is usually 30 parts by mass or less when the total amount of primary-tertiary amine and secondary-tertiary amine is 100 parts by mass.
Other catalysts include metal catalysts, quaternary ammonium salts, and the like. These may be used alone or in combination of two or more.

Examples of the metal catalyst include organic acid metal salts and organometallic complexes.
Examples of the metal species constituting the organic acid metal salt include sodium, potassium, calcium, iron, cobalt, nickel, zinc, zirconium, tin, lead, and bismuth. Further, examples of the organic acids constituting the organic acid metal salt include acetic acid, octylic acid, neodecanoic acid, naphthenic acid, and rosin acid. Specifically, sodium acetate, potassium acetate, potassium octylate, bismuth octylate, lead octylate, iron octylate, tin octylate, calcium octylate, zinc octylate, zirconium octylate, bismuth neodecanoate, zinc neodecanoate. , lead neodecanoate, cobalt neodecanoate, bismuth rosinate, dibutyltin dilaurate, and the like. These may be used alone or in combination of two or more.
Furthermore, examples of the metal species constituting the organometallic complex include iron, cobalt, nickel, zinc, zirconium, tin, lead, bismuth, and the like. Furthermore, examples of the ligand constituting the organometallic complex include acetylacetone and the like. Examples include iron acetylacetone, nickel acetylacetone, zinc acetylacetone, zirconium acetylacetone, and tin acetylacetone. These may be used alone or in combination of two or more.

Examples of the cation species constituting the quaternary ammonium salt include alkylammonium (tetramethylammonium, tetraethylammonium, etc.), hydroxyalkylammonium salt (hydroxypropyltrimethylammonium, hydroxyethyltrimethylammonium, etc.). As the anion species constituting the quaternary ammonium salt, only one type of these may be used or two or more types may be used in combination. The anion species constituting the quaternary ammonium salt include organic groups such as formic acid group, acetic acid group, 2-ethylhexanoic acid group, 2,2-dimethylpropanoic acid group, octylic acid group, and phosphoric acid ester group; halogen group , hydroxyl group, hydrogen carbonate group, carbonate group, and other inorganic groups. These may be used alone or in combination of two or more.

(4) Viscosity of Liquid A The viscosity of Liquid A of this composition is not limited and may be the same as or different from Liquid B, but the viscosity at 25°C must be 400 mPa・s or less. is preferable, 5 to 300 mPa·s is more preferable, and even more preferably 10 to 200 mPa·s. Within this range, workability is excellent in terms of appropriate injection pressure, and it is difficult to be diluted with water, allowing cleaner drainage.
The viscosity of liquid A can be measured at 25° C. using a B-type viscometer in accordance with JIS K7117-1.

[2] Liquid B (1) Polyisocyanate Liquid B contains "polyisocyanate." Polyisocyanate is an organic compound having two or more isocyanate groups (NCO groups) in the molecule. As the polyisocyanate, a monomer having two or more isocyanate groups (NCO groups) in the molecule may be used, or a multimer (prepolymer etc.) may be used. Furthermore, in the case of a multimer, the number of compounds (monomers) constituting the multimer may be one (mononuclear) or two or more (polynuclear). Furthermore, mixtures of monomers and multimers may be used. Examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like. These may be used alone or in combination of two or more.

As the aromatic polyisocyanate, diphenylmethane diisocyanate [2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate], tolylene diisocyanate [2,4-tolylene diisocyanate, 2,6 -tolylene diisocyanate], phenylene diisocyanate [1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate], xylylene diisocyanate [1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate], tetramethyl xylylene diisocyanate [1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate], 3,3'-dimethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate [1,5-naphthalene diisocyanate, etc.], diani Examples include cydine diisocyanate, isopropylidene bis[4-cyclohexyl isocyanate], triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris(isocyanate phenyl)-thiophosphoric acid, and the like. These may be used alone or in combination of two or more.

Examples of aliphatic polyisocyanates include hexamethylene diisocyanate [1,6-hexamethylene diisocyanate], trimethylhexamethylene diisocyanate [2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate], and lysine diisocyanate. , lysine triisocyanate, dimer acid diisocyanate, and the like. These may be used alone or in combination of two or more.
Examples of the alicyclic polyisocyanate include 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate [methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2, 6-diisocyanate], bis(isocyanatomethyl)cyclohexane [cis-1,3-(diisocyanatemethyl)cyclohexane, trans-1,3-(diisocyanatemethyl)cyclohexane, 1,4-(diisocyanatemethyl)cyclohexane], etc. It will be done. These may be used alone or in combination of two or more.
Further, the various monomers described above may be modified products thereof (such as modified isocyanurate products and carbodiimide modified products), blocked products thereof, hydrogenated products thereof, and the like. Alternatively, an isocyanate group-containing prepolymer obtained by reacting an active hydrogen group-containing compound and the polyisocyanate by a known method may be used. Each of these may be used alone or in combination of two or more.

As the polyisocyanate contained in liquid B of the present composition, aromatic polyisocyanates are preferable among those mentioned above from the viewpoint of the strength of the obtained foam and the reaction rate, and further, diphenylmethane diisocyanate (monomeric MDI, More preferred are polymeric MDI, crude MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate (IPDI). More preferably, diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI) is used.

The amount of polyisocyanate contained in the B liquid is not limited, and for example, the B liquid can be composed only of polyisocyanate. In this case, assuming that the entire B liquid is 100% by mass, the amount of polyisocyanate is 100% by mass. On the other hand, when adding other components other than polyisocyanate (for example, additives, etc.) to liquid B, the amount of polyisocyanate is preferably 85% by weight or more, and 90% by weight when the entire liquid B is 100% by weight. % or more, more preferably 91% by mass or more, particularly preferably 92% by mass or more. On the other hand, this content is usually 99.99% by mass or less, more preferably 99.8% by mass or less, even more preferably 99.6% by mass or less, and particularly preferably 99.4% by mass or less. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be 85-99.99% by mass, it can be 90-99.8% by mass, it can be 91-99.6% by mass, and it can be 82-99.4% by mass. It can be done.

(2) Viscosity of liquid B The viscosity of liquid B in this composition is not limited and may be the same as or different from liquid A, but the viscosity at 25°C must be 400 mPa·s or less. is preferable, 5 to 300 mPa·s is more preferable, and even more preferably 10 to 200 mPa·s. Within this range, workability is excellent in terms of appropriate injection pressure, and it is difficult to be diluted with water, allowing cleaner drainage.
The viscosity of liquid B can be measured at 25° C. using a B-type viscometer in accordance with JIS K7117-1.

[3] Other components Other components can be added to the A liquid and the B liquid of the present composition as necessary. Other components include foaming agents, foam stabilizers, flame retardants, viscosity modifiers (thinning agents, thickening agents, etc.). These may be used alone or in combination of two or more.

The foaming agent is a component that forms the foamed state of the resulting solidified body (foamed body). Although the type of blowing agent is not limited, examples of the blowing agent include inorganic blowing agents and organic blowing agents. These may be used alone or in combination of two or more. Examples of the inorganic blowing agent include water, carbon dioxide, and the like. Among these, water functions as a blowing agent in coexistence with polyisocyanate, so when water is used as a blowing agent in the present composition, it can be incorporated into liquid A. Furthermore, when a water-soluble silicate is used as water glass (silicate aqueous solution), the water constituting the water glass can function as a foaming agent. As the organic blowing agent, a fluorocarbon-free or fluorocarbon-based blowing agent can be used. The organic blowing agent is preferably fluorocarbon-free, and halogenated alkenes such as hydrofluoroolefins and hydrochlorofluoroolefins are more preferable.
When using a blowing agent, the amount of the blowing agent can be 0.01 to 50 parts by weight, and can be 0.1 to 25 parts by weight, assuming that the total polyisocyanate contained in the present composition is 100 parts by weight. , 0.5 to 10 parts by mass.

The foam stabilizer is a component that improves the uniformity of foam cells constituting the obtained solidified body (foamed body). The type of foam stabilizer is not limited, but examples of foam stabilizers include silicone foam stabilizers (silicone, etc.), nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymers, and polysiloxane oxyalkylene copolymers. Oxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, etc. can be used. These may be used alone or in combination of two or more.
When using a foam stabilizer, the amount of the foam stabilizer can be 0.05 to 5 parts by mass, and should be 0.1 to 4 parts by mass, assuming that the total polyisocyanate contained in the present composition is 100 parts by mass. The amount can be 0.1 to 3 parts by mass. Within this range, clean drainage is possible while obtaining an appropriate foam regulating effect.

The viscosity modifier is a component that can adjust the viscosity of the A liquid and/or the B liquid constituting the present composition. Although the type of viscosity modifier is not limited, examples of the viscosity modifier include a thinner, a thickener, and the like, and the thinner can be suitably used in the present composition. As the thinner, alcohols, ethers, esters, petroleum hydrocarbons, etc. can be used. These may be used alone or in combination of two or more.
Examples of alcohols include methanol, ethanol, propanol, isopropyl alcohol, butanol, and the like. Examples of ethers include ethyl cellosolve, butyl cellosolve, and the like. Examples of the esters include cyclic esters such as propylene carbonate; esters (non-cyclic esters) such as dicarboxylic acid methyl ester and ethylene glycol monomethyl ether acetate.
When using a viscosity modifier, if the total polyisocyanate contained in the present composition is 100 parts by mass, the viscosity reducing agent can be 0.1 to 15 parts by mass, and should be 0.5 to 10 parts by mass. The amount can be 1 to 8 parts by mass.

The flame retardant is a component that improves the flame retardancy of the obtained solid body (foam). The type of flame retardant is not limited, but flame retardants include phosphate esters (monophosphates, condensed phosphates, organic phosphate monoesters, organic phosphate diesters, organic phosphate triesters, monophosphates, pyrophosphates). salts, polyphosphates, organic phosphinates, etc.), red phosphorus, boron-based flame retardants, bromine-based flame retardants, chlorine-based flame retardants (halogenated paraffins, etc.), stannic acid metal salts, antimony-containing flame retardants, metal hydroxides Examples include metal compounds, hydrates of metal compounds, clay minerals, and the like. These may be used alone or in combination of two or more.
When using a flame retardant, the amount of the flame retardant can be 0.1 to 100 parts by mass, and can be 0.5 to 50 parts by mass, when the total polyisocyanate contained in the present composition is 100 parts by mass. , 1 to 10 parts by mass.

[4] Use of chemical composition for ground injection The use of the present composition is not limited, but due to its properties, it is particularly suitably used in the architectural and civil engineering field (architectural field and civil engineering field). That is, the present composition can be used as a chemical composition for ground injection in the field of construction and civil engineering. Among these, in the construction field, for example, flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, insulation materials for walls, insulation materials for ceilings, insulation materials for floors, structural It can be used for on-site spraying during manufacturing, filling internal gaps, reinforcing structures that have deteriorated over time, etc. In addition, in the civil engineering field, this composition is injected into the ground, underground, soil, ground, bedrock, gaps between these and structures (building structures), and even gaps within structures, etc., to form foams. By curing, the injection site can be filled and reinforced.

[2] Foam (foamed solidified body) and method for producing the same The foam of the present invention is characterized in that it is obtained by mixing liquid A and liquid B.
Mixing of liquid A and liquid B can be performed at the time of forming the foam. That is, the composition may be mixed before injection into the intended location, mixed during injection, or mixed after injection, or a combination of two or more of these may be used. More specifically, it is desirable that liquid A and liquid B be combined before the discharge nozzle of the piping and mixed immediately before being discharged. This makes it easier to control the mixing ratio within a desired range.

Further, the mixing ratio of liquid A and liquid B is not limited and can be set within an appropriate range depending on the physical properties of the foam formed by the reaction of liquid A and B, but usually, on a mass basis, The ratio of liquid A: liquid B is preferably 2:1 to 1:3, more preferably 1.5:1 to 1:2.

The expansion ratio of the foam obtained using the present composition is not limited, but in the range of 10 to 30°C, it is preferably 25 times or less, more preferably 22 times or less, even more preferably 20 times or less, and 18 times or less. It is particularly preferably 16 times or less, particularly preferably 16 times or less. On the other hand, the expansion ratio is more preferably 2 times or more, further preferably 4 times or more, particularly preferably 4.5 times or more, and particularly preferably 5 times or more. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be 2 to 22 times, 4 to 20 times, 4.5 to 18 times, and 5 to 16 times. Within these preferable ranges, the resulting foam can have sufficient strength while suppressing the influence of temperature in the foaming environment, and is also economically efficient.

In addition, when the foaming ratios of foams obtained using this composition were measured at 10°C, 20°C, and 30°C, it was found that among the foaming ratios at each temperature, the minimum foaming ratio was The ratio of expansion ratio (expansion ratio = minimum expansion ratio / maximum expansion ratio) is not limited, but is preferably 0.38 or more, more preferably 0.40 or more, even more preferably 0.42 or more, 0. 44 or more is particularly preferred, and 0.46 or more is particularly preferred. Ideally, the closer the expansion ratio is to 1.0, the more preferable it is. These upper and lower limit values can be arbitrarily combined. That is, for example, it can be set to 0.38 to 1.0, it can be set to 0.40 to 1.0, it can be set to 0.42 to 1.0, and it can be set to 0.44 to 1.0. It can be set to 0.46 to 1.0. Within these preferable ranges, the resulting foam can have sufficient strength while suppressing the influence of temperature in the foaming environment, and is also economically efficient.

Hereinafter, the present invention will be explained in more detail based on Examples, but these Examples are merely examples shown for convenience for explanation, and the present invention is not limited to these Examples in any way. It's not something you can do.

[1] Preparation of composition The following components were mixed in the combinations and formulations shown in Tables 1 to 3 below to prepare the ground having each of the A liquid and B liquid of Examples 1 to 21 and Comparative Examples 1 to 14. A drug composition for injection was obtained.

(1) Water-soluble silicate (silicate aqueous solution)
・No. 2 Sodium Silicate: No. 2 Sodium Silicate, manufactured by Fuji Chemical Co., Ltd., solid content 40%
・No. 1 Sodium Silicate: No. 1 Sodium Silicate, manufactured by Fuji Chemical Co., Ltd., solid content 48% (adjust the solid content to 40% by adding water before use)

(2) Polyol ・PP400: Polyether polyol (polypropylene glycol), manufactured by Sanyo Kasei Co., Ltd., product name "SANNIX PP-400", number average molecular weight 400, number of functional groups 2
・PB-700: Polyether polyol (polypropylene glycol), manufactured by NOF Corporation, product name "UNIOL PB-700", initiator butylene glycol, number average molecular weight 700, number of functional groups 2
・PP1000: Polyether polyol (polypropylene glycol), manufactured by Sanyo Kasei Co., Ltd., product name "SANNIX PP-1000", number average molecular weight 1000, number of functional groups 2
・TPG (Mn192): tripropylene glycol, Tokyo Chemical Industry Co., Ltd., number average molecular weight 192, number of functional groups 2
・DPG/TPG: dipropylene glycol (number average molecular weight 134, number of functional groups 2, Tokyo Chemical Industry Co., Ltd.) and tripropylene glycol (number average molecular weight 192, number of functional groups 2, Tokyo Chemical Industry Co., Ltd.) in a mass ratio of 3: Polyol mixture obtained by mixing in step 7

(3) Catalyst (3-1) First tertiary amine - Dimethylaminoethoxyethanol: 2-[2-(dimethylamino)ethoxy]ethanol (CAS RN: 1704-62-7), manufactured by Kao Corporation, product name "Kaolizer No. 26", OH group (available), dimethylamino group (available)
・Trimethylaminoethylethanolamine: 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS RN: 2212-32-0), manufactured by Tosoh Corporation, product name "Toyocat RX-5", OH group Co., Ltd., Dimethylamino Group Co., Ltd.
・Dimethylaminohexanol: 6-(dimethylamino)-1-hexanol (CAS RN: 1862-07-3), manufactured by Kao Corporation, product name "Kaolizer No. 25", OH group (with), dimethylamino group ( Yes)
・Diethylaminoethanol: 2-(diethylamino)ethanol (CAS RN: 100-37-8), manufactured by Tokyo Chemical Industry Co., Ltd., OH group (with), dimethylamino group (without)

(3-2) Second tertiary amine ・Tetramethylhexamethylenediamine: N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS RN: 111-18-2), Kao Corporation Manufactured by the company, product name "Kaolizer No. 1", OH group (no), dimethylamino group (with)
・Pentamethyldiethylenetriamine: N,N,N',N",N"-pentamethyldiethylenetriamine (CAS RN: 3030-47-5), manufactured by Kao Corporation, product name "Kaolizer No. 3", OH group (no ), dimethylamino group (available)
・Dimethylimidazole: 70% 1,2-dimethylimidazole (CAS RN: 1739-84-0) Ethylene glycol solution, manufactured by Kao Corporation, product name "Kaolizer No. 350", OH group (absent), dimethylamino group ( Nothing)
・Triethylenediamine: 33% triethylenediamine (CAS RN: 280-57-9) Dipropylene glycol solution, manufactured by Kao Corporation, product name "Kaolizer No. 31", OH group (absent), dimethylamino group (absent)

(4) Polyisocyanate ・MDI (M100): Polymeric MDI, manufactured by Kumho Mitsui Chemicals, product name "Cosmonate M100"
・MDI (M200): Polymeric MDI, manufactured by Kumho Mitsui Chemicals, product name "Cosmonate M200"
・Prepolymer: Prepolymer MDI, in-house synthesized product, reaction product obtained by adding 5 parts of the above "PP-1000" to 100 parts of the above "M100" and reacting at 70 ° C. for 3 hours.

(5) Foam stabilizer - Foam stabilizer: Polyether modified siloxane, manufactured by Momentive Performance Materials Japan LLC, product name "Niax Silicone L-6970")

(6) Thinning agent - Thinning agent: Propylene carbonate, manufactured by Tokyo Chemical Industry Co., Ltd.

(7) Flame retardant ・Flame retardant: Tris (chloropropyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[2] Measurement and evaluation (1) Measurement of viscosity of liquids A and B Using a B-type viscometer, the measurements of Examples 1 to 18 and Comparative Examples 1 to 12 were carried out at 25°C in accordance with JIS K7117-1. The viscosity of liquid A and liquid B constituting each drug composition for ground injection was measured. The results are shown in Tables 1 to 3.

(2) Foaming evaluation Using the chemical compositions for ground injection of Examples 1 to 21 and Comparative Examples 1 to 14 obtained in [1] above, foams were prepared in the following manner, and the foaming ratio and foaming Body appearance was measured and evaluated.

(2-1) Production of foam (foaming in air) From each of the chemical liquid compositions for ground injection of Examples 1 to 21 and Comparative Examples 1 to 14, the mass ratio of liquid A and liquid B was 1:1, In addition, liquid A and liquid B were separated so that the total volume of liquid A and liquid B was 100 mL. After adjusting the temperature of these A and B solutions to 10°C, they were put into a 1L cup, stirred (hand mixed) at 400 rpm for 10 seconds, and then foamed in the air to obtain a foam. Ta.
Furthermore, a foam was produced in the same manner except that the foam production temperature was changed from 10°C to 20°C.
Furthermore, a foam was produced in the same manner except that the foam production temperature was changed from 10°C to 30°C.

(2-2) Measurement of expansion ratio In (2-1) above, foams obtained in a 10°C environment, foams obtained in a 20°C environment, and foams obtained in a 30°C environment. The expansion ratio of each of the foams was measured by the following method and shown in Tables 1 to 3 as "expansion ratio 10°C", "expansion ratio 20°C", and "expansion ratio 30°C". In addition, the ratio of the smallest foaming ratio (minimum foaming ratio/maximum foaming ratio) to the largest foaming ratio among the foaming ratio at 10°C, the foaming ratio at 20°C, and the foaming ratio at 30°C was calculated, and the ” as shown in Tables 1 to 3.
Measurement of foaming ratio: The height of the liquid level of the mixed liquid in the cup when liquid A and liquid B were mixed in the cup was measured as H1. Next, foaming was started and the height of the top of the foam formed in the cup was measured as the maximum foaming height. Thereafter, the height of the foam at the end of the curing reaction was measured as H2. Next, the foaming ratio was calculated as H2/H1 using the measured values of H1 and H2. In addition, each height at the time of measurement was measured visually using a gauge.

(2-3) Appearance evaluation of foam The foam obtained in the above (2-1) at 10°C, the foam obtained at 20°C, and the foam obtained at 30°C The appearance of each of the obtained foams was evaluated according to the following criteria and is shown in Tables 1 to 3.
"○": Foam cells are fine and the foam is good.
"Δ": Shrinkage of 15% to 30% from the maximum foaming height was observed.
"×": Appearance defects corresponding to one or more of the following are observed: shrinkage of more than 30% from the maximum foam height, a large cavity is formed in the center, and rough foam cells. Ta.

(2-4) Preparation of foam (foaming in water) 1000 ml of water was dispensed into a 2 L cup, and the water temperature in the cup was adjusted to 20°C. On the other hand, from each drug composition for ground injection of Example 1 and Examples 10 to 15, the mass ratio of liquid A and liquid B was 1:1, and the total volume of liquid A and B was 100 mL. In this way, liquid A and liquid B were separated. After adjusting the temperature of these A liquid and B liquid to 20°C, they were put into one cup, and after stirring (hand mixing) at 400 rpm for 10 seconds, the above 20°C water was contained. A mixture of liquids A and B was poured into a cup and foamed in water.

(2-5) Evaluation of water turbidity due to foaming in water After waiting for the foaming process in (2-4) above to finish, the state of the water used as a reaction environment was observed and evaluated according to the following criteria, and the results are shown in Table 4. Indicated.
"○": Almost no water turbidity is observed.
"△": Slight water turbidity is observed.
"×": Water turbidity is observed.

(2-6) Evaluation of defoaming time due to foaming in water Furthermore, water 1 hour after the completion of foaming (water used as reaction environment) was collected in a 500ml transparent polyethylene container with a lid, and shaken for 10 seconds. Foaming was observed and evaluated according to the following criteria, and the results are shown in Table 4.
"◎": Foaming disappeared within 10 seconds.
"○": Defoaming occurred within more than 10 seconds and within 30 seconds.
"Δ": Defoaming occurred within more than 30 seconds and within 60 seconds.
"x": Foaming remains even after 60 seconds or more.

[3] Effects of Examples From Tables 1 to 3, it can be seen that the compositions of Comparative Examples 1 to 4 and 9, in which liquid A did not contain secondary or tertiary amines, had insufficient foaming stability and Shrinkage and coarsening are observed in the foam. It can also be seen that the expansion ratio is small and is influenced by temperature. In addition, the compositions of Comparative Examples 5 to 8 and 11 in which the liquid A did not contain primary-tertiary amines had insufficient foaming stability, and the resulting foams suffered from shrinkage, cavitation, or coarsening. Is recognized. Furthermore, it can be seen that the expansion ratio is small and is influenced by temperature. Furthermore, in Comparative Example 10 in which the liquid A did not contain any primary to tertiary amine, a stable foam was obtained, but the foaming ratio was small and it was found that it was affected by temperature. Furthermore, in the compositions of Comparative Example 12, in which the polyol was not contained in the A liquid, and in Comparative Examples 13 and 14, in which Mn≦200 even when the polyol was contained, the foaming ratio was small and was affected by temperature. I understand.
On the other hand, in the compositions of Examples 1 to 21 in which the liquid A contained a water-soluble silicate, a polyol with Mn>200, a primary-tertiary amine, and a secondary-tertiary amine, good foaming was achieved. It can be seen that while maintaining a high magnification, the dependence on the reaction temperature can be reduced and defective foaming can be prevented.

It is suitably used in the architectural and civil engineering fields (architectural and civil engineering fields), etc. Among these, in the construction field, for example, filler foam for walls, filler foam for ceilings, filler foam for floors, insulation materials for walls, insulation materials for ceilings, insulation materials for floors, and internal gaps during structure manufacturing. It can be used for filling structures, reinforcing structures that have deteriorated over time, etc. In addition, in the civil engineering field, this composition is injected into the ground, underground, soil, ground, bedrock, gaps between these and structures (building structures), and even gaps within structures, etc., to form foams. By curing, the injection site can be filled and reinforced.

Claims (10)

A chemical liquid composition for ground injection consisting of two types of chemical liquids, liquid A and liquid B,
The liquid A contains a water-soluble silicate, a polyol, and a catalyst,
The B liquid contains polyisocyanate,
The catalyst includes two types of tertiary amines, a first tertiary amine having a hydroxy group and a second tertiary amine not having a hydroxy group,
A chemical composition for ground injection, wherein the polyol is a polyol having a number average molecular weight of more than 200. The chemical composition for ground injection according to claim 1, wherein the polyol is a polyether polyol. The chemical composition for ground injection according to claim 2, wherein the polyether polyol includes a polyether polyol having a number average molecular weight of more than 200 and less than 500, and a polyether polyol having a number average molecular weight of 500 or more. The chemical composition for ground injection according to any one of claims 1 to 3, wherein the polyol is 8% by mass or less based on 100% by mass of the entire liquid A. The liquid chemical composition for ground injection according to any one of claims 1 to 4, wherein the first tertiary amine does not have a ring structure in its main chain comprising a tertiary amino group and the hydroxyl group. The chemical liquid for ground injection according to any one of claims 1 to 5, wherein the first tertiary amine has an oxygen atom and/or a nitrogen atom in a main chain comprising a tertiary amino group and the hydroxyl group. Composition. The chemical composition for ground injection according to any one of claims 1 to 6, wherein the first tertiary amine has a dimethylamino group. The chemical composition for ground injection according to any one of claims 1 to 7, wherein the second tertiary amine does not have a ring structure. A foam obtained by mixing the liquid A and the liquid B constituting the chemical composition for ground injection according to any one of claims 1 to 8. A method for manufacturing a foam, comprising mixing the liquid A and the liquid B constituting the chemical composition for ground injection according to any one of claims 1 to 8 to form a foam.