JP7088788B2 - Chemical composition for polyurethane foam - Google Patents

Description

The present invention relates to a chemical solution composition for polyurethane foam, and more particularly to a chemical solution composition for polyurethane foam, which is advantageously used in an injection backfilling method or the like in tunnel construction.

Polyurethane foam has been widely used in the fields of civil engineering and construction because it has excellent heat insulating properties and adhesiveness and is relatively lightweight. For example, in tunnel construction, a mixed solution containing a polyol, polyisocyanate, a catalyst, etc. is injected into the voids created between the tunnel lining and the ground on the back surface and the voids left behind during construction, and the inside of the voids. A construction method (injection backfilling construction method) is known that aims to secure the thickness of the lining and to equalize the earth pressure applied to the lining to prevent the tunnel from collapsing by foaming and hardening in the tunnel. ..

Polyurethane foams used in various forms in various construction methods in the civil engineering field such as the above-mentioned injection backfilling method, or in the construction field and other fields, and various manufacturing methods thereof have been conventionally used. Has been proposed.

For example, in Patent Document 1 (Japanese Unexamined Patent Publication No. 8-268151), as a method for producing a polyurethane foam by foaming a polyisocyanate and a polyol in a closed system mold, the weight of the polyol is predetermined. Disclosed is a method comprising essential use of a proportionate amount of an alkylene (2-4 carbon atoms) carbonate and a predetermined formate-containing composition. Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2010-53268), a polyol compound containing an aromatic polyester polyol in a predetermined ratio and a phosphoric acid ester flame retardant in a predetermined ratio as a polyol composition for a rigid polyurethane foam. The composition contained in the above is disclosed.

However, when a thick block-shaped polyurethane foam is produced according to the method disclosed in Patent Document 1, the reaction heat generated when the polyol and the polyisocyanate react with each other is accumulated inside the polyurethane foam, and the heat causes the polyurethane foam. There is a risk that the inside of the polyurethane foam will burn and the entire polyurethane foam will turn yellow (scorch), and in some cases the polyurethane foam will self-ignite. Further, when a thick block-shaped polyurethane foam is produced using the composition for rigid polyurethane foam disclosed in Patent Document 2, cracks may occur inside the polyurethane foam due to heat shrinkage or strain.

Japanese Unexamined Patent Publication No. 8-268151 Japanese Unexamined Patent Publication No. 2010-53268

Here, the present invention has been made in the background of such circumstances, and the problem to be solved thereof is the generation of scorch due to the heat of reaction even when a relatively thick polyurethane foam is produced. It is an object of the present invention to provide a chemical liquid composition for polyurethane foam, which can advantageously suppress the risk of self-ignition, further reduce the occurrence of cracks inside the foam due to heat shrinkage and strain.

The present invention can be suitably carried out in various aspects as listed below in order to solve the above-mentioned problems, and each of the embodiments described below can be performed in any combination. It can be adopted. It should be noted that the aspects or technical features of the present invention are not limited to those described below, and are understood based on the invention idea grasped from the description of the entire specification. It should be.

(1) In a chemical solution composition for polyurethane foam composed of a solution A containing a polyol as a main component and a solution B containing a polyisocyanate as a main component, the polyol has i) a hydroxy acid base value of 30 to 700 mgKOH / g. A polyether polyol containing a certain polyether polyol in a proportion of 90% by mass or more, and ii) a polyether polyol in which 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide is 60% by mass or more. 1 or 2 selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, styrene carbonate, isobutylene carbonate, dimethyl carbonate, diethyl carbonate, dit-butyl dicarbonate and diphenyl carbonate. The above - mentioned carbonate compounds and phosphate esters are independently contained in at least one of the solutions A and B , and the carbonate compound is 100 parts by mass of the polyol. A chemical solution composition for polyurethane foam, characterized in that it is contained in a proportion of 0.3 to 12 parts by mass .
(2) The chemical solution composition for polyurethane foam according to the above aspect (1 ), wherein the phosphoric acid ester is contained in a ratio of 20 to 70 parts by mass with respect to 100 parts by mass of the polyol.
(3) The embodiment (1) or the embodiment (2) , wherein the polyether polyol contains polypropylene glycol obtained by using any one of propylene glycol, glycerin or bisphenyl A as an initiator and adding propylene oxide to the initiator. The chemical composition for polyurethane foam described in.
(4) The chemical composition for polyurethane foam according to the above-mentioned embodiment (3) , wherein the polyether polyol further contains polypropylene glycol obtained by using ethylenediamine as an initiator and adding propylene oxide to the polyether polyol.
(5) The chemical composition for polyurethane foam according to any one of the above embodiments (1) to (4) , wherein the polyol contains a Mannich-based polyether polyol in a proportion of 10 to 40% by mass.
(6) The chemical composition for polyurethane foam according to any one of the above-mentioned aspects (1) to (5) above, wherein the carbonate compound is propylene carbonate.
(7) The chemical liquid composition for polyurethane foam according to any one of the above-mentioned embodiments (1) to (6) , wherein the catalyst is contained in the liquid A.
(8) The chemical solution composition for polyurethane foam according to the above aspect (7) , wherein the catalyst contains a metal acetate.
(9) The chemical composition for polyurethane foam according to the above aspect (8) , wherein the metal acetate is potassium acetate.
(10) Any of the above-mentioned embodiments (1) to (9) in which water as a foaming agent is contained in the liquid A at a ratio of 1 to 10 parts by mass with respect to 100 parts by mass of the polyol. The chemical composition for polyurethane foam according to one.

Then, according to the composition of the chemical liquid composition for polyurethane foam according to the present invention, various effects as listed below can be exhibited.
(1) The carbonate compound, which is an essential component in the chemical composition for polyurethane foam of the present invention, a) functions as a foaming aid when the polyol and polyisocyanate react with each other, and carbon dioxide gas is released earlier in such reaction. In Therefore, since the uniformity of cells in the foam is improved, for example, even when used in various applications for forming a thick-walled molded body (foam), such a molded body (foam). The occurrence of cracks inside the is suppressed.
(2) Since the reaction from foaming to curing in the mixed solution of the solution A and the solution B proceeds rapidly by the carbonate compound, the amount of the catalyst used can be reduced as a result, and the present invention. Since the chemical composition for polyurethane foam of the present invention also contains flame-retardant ester phosphate, such a molded product (foam) can be produced even when a thick-walled molded product (foam) is produced. Foam) The generation of scorch inside is effectively suppressed.
(3) In the chemical composition for polyurethane foam of the present invention, a polyol containing a polyether polyol having predetermined characteristics is regarded as an essential component together with a carbonate compound and a phosphoric acid ester as a polyol. By using a special polyol in combination with a carbonate compound and a phosphoric acid ester, the generation of cracks and scorch inside the above-mentioned molded product (foam) can be more effectively suppressed.

In short, the present invention relates to a two-component polyurethane foam chemical solution composition (hereinafter, also simply referred to as a chemical solution composition), which comprises a solution A containing a polyol as a main component and a solution B containing a polyisocyanate as a main component. As the main component of the solution A, one or more of the polyether polyols having predetermined characteristics are used in a predetermined ratio, and at least one of the solution A and the solution B contains a carbonate compound and a carbonate compound. It is composed of a phosphoric acid ester. In the following, first, the essential components in the chemical composition of the present invention will be described in detail.

(Polyol)
In the chemical solution composition for polyurethane foam according to the present invention, the polyol which is the main component of the solution A contains i) a polyether polyol having a hydroxyl value of 30 to 700 mgKOH / g in a proportion of 90% by mass or more. In addition, ii) contains a polyether polyol in which 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide in a proportion of 60% by mass or more. The object of the present invention is effectively achieved by using a polyol containing a polyether polyol having such a predetermined property in a predetermined ratio in combination with a carbonate compound and a phosphoric acid ester described later.

Specifically, when a polyol containing a polyether polyol having a hydroxyl value of 30 to 700 mgKOH / g in a proportion of less than 90% by mass is used as the polyol in the present invention, cracks and cracks occur in the obtained foam. There is a risk that the occurrence of scorch (a phenomenon in which the inside of polyurethane foam is burnt by the heat of reaction and the entire polyurethane foam turns yellow) cannot be effectively suppressed. The hydroxyl value of the polyether polyol contained in a proportion of 90% by mass or more of the polyol is 30 to 700 mgKOH / g, preferably 100 to 600 mgKOH / g, and more preferably 200 to 550 mgKOH / g. If a polyether polyol having a hydroxyl value of less than 30 mgKOH / g is used, the object of the present invention may not be sufficiently achieved, for example, cracks are likely to occur inside the foam, while the hydroxyl value is 700 mgKOH / g. If more than the amount of the polyether polyol is used, cracks and scorch may easily occur inside the foam.

Further, even when a polyol containing a polyether polyol in which 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide in a proportion of less than 60% by mass is used as the polyol in the present invention. There is a risk that the occurrence of cracks and scorch cannot be effectively suppressed.

By the way, the polyether polyol generally uses a compound having at least two or more active hydrogen groups, for example, polyhydric alcohols, aliphatic amines, aromatic amines, Mannig condensate and the like as an initiator, and is used for this. , It is produced by an addition reaction or an addition polymerization reaction consisting of addition of an alkylene oxide such as ethylene oxide or propylene oxide. Specific examples of the polyvalent alcohols used in the production thereof include 1) ethylene glycol, propylene glycol, 1,2-butanediol, and 1,3-butanediol as the polyvalent alcohols. , 1,4-Butanediol, 2,3-Butanediol, 1,2-hexanediol, 1,6-hexanediol, 10-decanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol , 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, glycerin, trimethylolpropane, pentaerythritol, diglycerin, glucose, mannose, sorbitol, mannitol, sorbitan, dipentaerythritol, fructose , Scruose, methyl glucoside, etc. 2) Examples of aliphatic amines include ethylenediamine, propylenediamine, butylene diamine, pentamethylenediamine, hexamethylenediamine, alkylenediamines such as neopentyldiamine, alkylenetriamines such as diethylenetriamine, and further. 3) Arcanol amines such as ethanolamine, diethanolamine, triethanolamine, etc. 3) As aromatic amines, 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'- Diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, naphthalenediamine, etc. 4) Mannig condensates include phenols such as phenol, nonylphenol, cresol, bisphenol A and resorcinol, and formaldehyde and para. Examples of compounds obtained by reacting aldehydes such as formaldehyde with alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol and aminoethylethanolamine shall be exemplified. Can be done.

Among the above-mentioned polyether polyols, in the present invention, polypropylene glycol (hereinafter referred to as polyether polyol α) obtained by using any one of propylene glycol, glycerin or bisphenol A as an initiator and adding propylene oxide to the initiator is used. , Used to advantage. When two or more kinds of polyether polyols are used, it is preferable to adjust the usage amount (usage ratio) of the polyether polyol α to be larger than the usage amount (usage ratio) of the other polyether polyols.

When the above-mentioned polyether polyol α is used, polypropylene glycol (hereinafter referred to as polyether polyol β) obtained by using ethylenediamine as an initiator and adding propylene oxide to the polyether polyol α is used in combination with the polyether polyol α. Is preferable. By using this polyether polyol β, the generation of cracks inside the foam can be suppressed more effectively, and the strength of the obtained foam can be advantageously improved. When the polyether polyol β is used, its usage ratio is 10 to 40% by mass, preferably 20 to 35% by mass in the polyol. When the usage ratio of the polyether polyol β in the polyol is less than 10% by mass, the effect of using the polyether polyol β is not recognized, while when the usage ratio exceeds 40% by mass, the water resistance of the obtained foam becomes high. There is a risk of deterioration.

On the other hand, in the present invention, a Mannig-based polyether polyol (a polyether polyol obtained by adding an alkylene oxide to a Mannig condensate) is used in a proportion of 10 to 40% by mass, preferably in a proportion of 20 to 35% by mass. , The contains polyol is advantageously used. When a polyol containing a Mannig-based polyether polyol is used, the reaction rate between the polyol and the polyisocyanate becomes faster, so that the amount of catalyst used can be reduced, and by reducing the amount of catalyst used, the amount inside the foam can be reduced. The generation of scorch can be suppressed more effectively. When the usage ratio of the Mannich-based polyether polyol is less than 10% by mass in the polyol, the above-mentioned effect cannot be enjoyed, while when the usage ratio exceeds 40% by mass, the obtained foam Water resistance may decrease.

The above-mentioned polyether polyol generally has a molecular weight of about 200 to 4000, more preferably 250 to 3200, and particularly preferably about 300 to 2000. It is even more desirable to have a molecular weight. When the molecular weight is smaller than 200, it is easily diluted with water and may cause cloudiness of water, and when the molecular weight is larger than 4000, it may be difficult to develop sufficient strength in the foam.

(Polyisocyanate)
The polyisocyanate, which is the main component of the liquid B, reacts with the polyol in the liquid A to form a polyurethane (resin), and is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule. Is. Specifically, aromatic polyisocyanates such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and isophorone diisocyanates. In addition to the alicyclic polyisocyanate such as, a urethane prepolymer having an isocyanate group at the molecular terminal, an isocyanurate-modified form of polyisocyanate, a carbodiimide-modified form, and the like can be exemplified. These polyisocyanate compounds may be used alone or in combination of two or more. In general, polymethylene polyphenylene polyisocyanate (crude MDI) is preferably used from the viewpoint of reactivity, economy, handleability and the like.

The blending ratio of the liquid B containing the polyisocyanate and the liquid A described above will be appropriately determined depending on the type of foam to be formed (for example, polyurethane or polyisocyanurate), but is generally a volume. The ratio is appropriately determined so as to be in the range of liquid A: liquid B = 1: 1 to 3.

(Carbonate compound)
In the chemical liquid composition for polyurethane foam according to the present invention, by containing the carbonate compound, foaming when the liquid A and the liquid B are mixed is improved, and the curing of the mixed liquid (formation of foam) is advantageous. It is accelerated, and the mixing property of the mixed solution is improved, so that the homogenization of cells in the foam is advantageously improved. Therefore, for example, even when the chemical composition of the present invention is used in various applications for forming a thick-walled molded product (foam), cracks occur inside the molded product (foam). Will be suppressed advantageously.

Examples of the carbonate compound used in the present invention include ethylene carbonate, propylene carbonate, butylene carbonate, styrene carbonate, isobutylene carbonate, dimethyl carbonate, diethyl carbonate, dit-butyl dicarbonate, diphenyl carbonate and the like. From these, one kind or two or more kinds are appropriately selected and used. Among these carbonate compounds, propylene carbonate is particularly advantageously used in the present invention, and by using propylene carbonate, the effects of the present invention can be enjoyed more advantageously.

In the present invention, the above-mentioned carbonate compound is used in a proportion of 0.3 to 12 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 with respect to 100 parts by mass of the polyol. It is blended in the liquid B in a proportion of up to 5 parts by mass. Even if the carbonate compound is blended in a ratio of less than 0.3 parts by mass with respect to 100 parts by mass of the polyol, the blending effect of the carbonate compound (prevention of cracks in the foam), which is the object of the present invention, is not sufficiently exhibited. On the other hand, even if the carbonate compound is blended in a proportion exceeding 12 parts by mass, the effect commensurate with the increase in the blending amount is not observed, and it is not a good idea. In the present invention, the carbonate compound may be contained in either liquid A containing a polyol as a main component or liquid B containing polyisocyanate as a main component, and may be blended in both liquid A and liquid B. Is also possible.

(Phosphate ester)
In the polyurethane foam chemical solution composition of the present invention, even when a thick-walled molded body (foam) is produced using the chemical solution composition by containing a phosphoric acid ester, the molded body (foam). ) The generation of scorch (a phenomenon in which the inside of the polyurethane foam is burnt by the heat of reaction and the entire polyurethane foam turns yellow) is effectively suppressed. The phosphoric acid ester used in the present invention is not particularly limited, and known ones such as monophosphoric acid ester and condensed phosphoric acid ester can be used alone or in combination.

Specifically, among these phosphate esters, the monophosphate ester is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, tri. Phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, Di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, Dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphinoxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resilcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (1-Chloro-2-propyl) phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) dichloroisopentyldiphosphate, 2,2-bis (chloromethyl) -1,3- Propanebis (chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (tribromoneopentyl) phosphate, 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate), poly Oxyalkylene bisdichloroalkyl phosphate and the like can be mentioned.

The condensed phosphate ester is not particularly limited, but for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.). ), Hydroquinonepoly (2,6-xylyl) phosphate, and condensed phosphate esters such as condensates thereof.

Further, as commercially available condensed phosphate esters, for example, resorcinol polyphenyl phosphate (CR-733S manufactured by Daihachi Chemical Industry Co., Ltd.), bisphenol A polycresyl phosphate (CR-741 manufactured by Daihachi Chemical Industry Co., Ltd.), and fragrance. Group Condensed Phosphate (CR-747 manufactured by Daihachi Chemical Industry Co., Ltd.), Resolsinol Polyphenyl Phosphate (Adecastab PFR manufactured by ADEKA Co., Ltd.), Bisphenol A Polycresyl Phosphate (Adecastab FP-600 manufactured by ADEKA Co., Ltd., FP- 700), Non-halogen condensed phosphate ester (DAIGURD-580, DAIGURD-610 manufactured by Daihachi Chemical Industry Co., Ltd.), Halogen-containing condensed phosphoric acid ester (CR-504L, CR-570 manufactured by Daihachi Chemical Industry Co., Ltd.), The same DAIGURD-540) and the like can be mentioned.

Among the above, it is preferable to use a monophosphate ester having a high effect of reducing the calorific value at the initial stage of the reaction between the solution A (polyol) and the solution B (polyisocyanate), and particularly tris (1-chloro-2-propyl). It is preferable to use phosphate.

The above-mentioned phosphoric acid ester is used in the composition for a polyurethane foam of the present invention in a proportion of 20 to 70 parts by mass, preferably 30 to 60 parts by mass with respect to 100 parts by mass of the polyol. .. If the ratio of the phosphoric acid ester to 100 parts by mass of the polyol is less than 20 parts by mass, scorch may be generated in the obtained foam, and sufficient flame resistance may not be imparted to the foam. On the other hand, if the usage ratio exceeds 70 parts by mass, the strength of the foam is lowered, which may cause cracks. In the present invention, the phosphoric acid ester may be contained in either the liquid A containing a polyol as a main component or the liquid B containing a polyisocyanate as a main component, as in the above-mentioned carbonate compound, and the liquid A may be contained. It is also possible to add it to both liquid B and liquid B.

The chemical solution composition for polyurethane foam according to the present invention requires the above-mentioned four components, but the chemical solution composition of the present invention has been conventionally blended with the chemical solution composition in addition to the above-mentioned essential components. It is possible to add a foaming agent, a catalyst, and various other additives.

(Effervescent agent)
In the present invention, from various conventionally known foaming agents, those that do not impair the object of the present invention can be appropriately selected and used. In particular, in the chemical composition for polyurethane foam of the present invention, a non-fluorocarbon foaming agent (and / or a source thereof) is advantageously used, and specifically, hydrocarbon (HC), hydrofluorocarbon (HFC), and the like. Organic foaming agents such as hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), such as halogenated alkenes (halogenated olefins), are suitable. Examples of these organic foaming agents include propane, normal pentane, isopentane, cyclopentane, butane, isobutane, hexane, isohexane, neohexane, heptane, and isoheptane as hydrocarbons (HC). Hydrofluorocarbons (HFCs) include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,2, 2-Tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,2,2,3 , 4, 5, 5, 5-decafluoropentane (HFC4310mee), dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like.

Alkene halides (halogenated olefins) also include those called hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), and generally contain chlorine or fluorine as a halogen. It is an unsaturated hydrocarbon derivative having about 2 to 6 carbon atoms. For example, propene, butene, pentene and hexene having 3 to 6 fluorine substituents, including tetrafluoropropene, pentafluoropropene and hexafluorobutene, as well as fluorochloropropene, trifluoromonochloropropene, fluorochlorobutene. Such as unsaturated hydrocarbons having a fluorine substituent and a chlorine substituent, and a mixture of two or more thereof can be mentioned. Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropene such as 3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye), trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf) , Tetrafluorobutene isomers (HFO1354), pentafluorobutene isomers (HFO1345), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) and other hexafluorobutene isomers (HFO1336mzz). HFO1336), heptafluorobutene isomer (HFO1327), heptafluoropentene isomer (HFO1447), octafluoropentene isomer (HFO1438), nonafluoropentene isomer (HFO1429) and the like can be mentioned. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), and the like. Dichlorotrifluoropropene (HCFO1223), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 2-chloro- 1,3,3-Trifluoropropene (HCFO-1233xe), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 3-chloro-1,2,3-trifluoropropene (HCFO-) 1233ye), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc) and the like can be mentioned.

In particular, the above-mentioned hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) have a low global warming potential due to their chemical instability, and therefore have received attention as environmentally friendly foaming agents. However, there is also an inherent risk of decomposition by a catalyst (a catalyst used to accelerate the reaction of polyols with polyisocyanates). However, in the present invention, since the amount of the catalyst contained in the chemical solution composition can be reduced as much as possible by the carbonate compound, decomposition of such a foaming agent (particularly HCFO-1233zd) can be achieved. It has the advantage that its foaming function can be advantageously exerted without fear of.

The amount of the organic foaming agent (HFC, HC, HFO, HCFO) used is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol in the liquid A. Is preferable. When the amount of the organic foaming agent used exceeds 50 parts by mass, the core density of the foam becomes low, which may cause a decrease in the strength of the foam and a deterioration in dimensional stability. There is also a problem of disadvantage in terms of cost. On the other hand, if the amount of the organic foaming agent used is less than 5 parts by mass, the function as a foaming agent cannot be fully exerted, the density of the obtained foam may increase, and the liquid A may be used. As the viscosity of the liquid B increases and the mixing property with the liquid B deteriorates, a problem that a good spray pattern cannot be obtained, for example, in the spray method is caused.

Further, in the present invention, water as a foaming agent can be used together with the above-mentioned organic foaming agents (HFC, HC, HFO, HCFO) or in place of such organic foaming agents. When water is used as a foaming agent, it is generally blended in liquid A containing a polyol as a main component in consideration of the reactivity between water and polyisocyanate, but water is present in liquid A. As a result, when the liquid A and the liquid B are mixed and reacted, the water reacts with the polyisocyanate in the liquid B to generate carbon dioxide, and the reaction heat is generated. Therefore, the heat can effectively promote the urethanization reaction and the isocyanurate-forming reaction, and the compressive strength of the obtained polyurethane foam can be further increased. Then, when the liquid A and the liquid B are mixed and reacted due to the presence of water in such a polyol composition, carbon dioxide is generated by the reaction between the water and the polyisocyanate in the liquid B. This carbon dioxide also contributes to the foaming of polyurethane. Moreover, when the organic foaming agent (HFC, HC, HFO, HCFO) is used in combination with water, an endothermic reaction occurs when the organic foaming agent volatilizes, but water reacts with polyisocyanate to generate carbon dioxide. The heat of reaction is generated when the heat of reaction is generated, which has the advantage that the organic foaming agent is likely to volatilize, thereby reducing the amount of the organic foaming agent used and reducing its cost. There will also be benefits to be gained.

The water as a foaming agent is contained in a proportion of 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of the polyol in the liquid A. If the amount of this water used is more than 10 parts by mass with respect to 100 parts by mass of the polyol, the strength will rather decrease. The reason is that the urea bond generated by the reaction between water and polyisocyanate increases in the resin, and the polyisocyanate used for the isocyanurate-forming reaction is consumed in the reaction with water, so that the polyisocyanate in the reaction system decreases. Because. Further, if the amount of such water used is less than 1 part by mass, the effect as a foaming agent due to the inclusion of water may not be sufficiently obtained.

Further, as described above, when the organic foaming agent (HFC, HC, HFO, HCFO) is used in combination with water, the mass ratio of the organic foaming agent and water is 60:40 to 99: 1, preferably 70: It is desirable to use it in a ratio of 30 to 95: 5. If the proportion of water exceeds 40 outside this range, brittleness develops as the reaction progresses, the adhesiveness to the skeleton surface decreases, and problems such as peeling may occur. In addition, carbon dioxide generated by the reaction with isocyanate may reduce the thermal conductivity and form a foam layer having an insufficient thermal conductivity.

(catalyst)
In the chemical liquid composition for polyurethane foam according to the present invention, it is possible to contain the catalyst in the liquid A containing a polyol as a main component, as in the conventional case.

In the present invention, any catalyst that contributes to the reaction between the polyol and the polyisocyanate can be used, and as such a catalyst, a tertiary amine catalyst, a metal catalyst, or the like can be used. It can be exemplified.

The tertiary amine catalyst is a foaming catalyst having an action of promoting the reaction between polyisocyanate and water when foaming is intended by contact with water, and promotes the reaction between polyisocyanate and polyol. There are a resination catalyst having an action, an isocyanurate-forming catalyst (triquantization catalyst) having an action to promote the trimerization of polyisocyanate, and the like.

Specifically, as the foaming catalyst, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N'-triethylaminoethylethanolamine, bis (dimethylaminoethyl) ether, N , N', N'-trimethylaminoethylpiperazine, N, N-dimethylaminoethoxyethanol, triethylamine and the like. The resinification catalyst includes N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropanediamine, N, N, N', N'-tetramethylhexane. Diamine, triethylenediamine, 33% triethylenediamine / 67% dipropylene glycol, N, N-dimethylaminohexanol, N, N-dimethylaminoethanol, N-methyl-N-hydroxyethylpiperazine, N-methylmorpholin, 1- Examples thereof include methylimidazole and 1,2-dimethylimidazole. Further, examples of the isocyanurate-forming catalyst include 2,4,6-tris (dimethylaminomethyl) phenol, N, N', N "-tris (3-dimethylaminopropyl) -hexahydro-s-triazine and the like. These may be used alone or in combination of two or more. Among them, a resinification catalyst and an isocyanurate-forming catalyst (trimerization catalyst) are preferably used, and in particular, isocyanate. By using a nucleolation catalyst (trimerization catalyst), the flame retardancy of the foam can be further improved by the nucleolation, and the generation of cracks inside the foam can be suppressed more effectively.

On the other hand, as the metal catalyst, known ones can be used without particular limitation, for example, organic acid metal salts such as sodium, potassium, calcium, tin, lead, bismuth, zinc, iron, nickel, zirconium, cobalt and organic. A metal complex can be used. Among them, examples of the organic acid metal salt include salts of acetic acid, octyl acid, neodecanoic acid, naphthenic acid, loginic acid and the like with the above metal, and examples of the organic metal complex include a complex of acetylacetone and the like with the above metal. Can be mentioned. 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, dibutyltin dioctate, dibutyltin dilaurylate; acetylacetone iron, acetylacetone zinc, acetylacetone zirconium, acetylacetone nickel, acetylacetone tin and the like. These metal salts and metal complexes may be used as those dissolved in a diluent such as mineral spirits, organic acids, glycols and esters in order to improve their handleability. Further, these metal catalysts may be used alone or in combination of two or more. Among these, metal acetate salts of lithium, sodium, potassium, rubidium, cesium, tin, lead, bismuth or zinc are preferable, alkali metal acetate salts are more preferable, and potassium acetate is particularly preferable.

Among such various catalysts, in the present invention, those containing a metal acetate salt, in other words, a metal acetate salt and another catalyst are preferably used together as a catalyst. As described above, by using the metal acetate and another catalyst in combination, the effect of the present invention can be enjoyed more advantageously.

Further, in the present invention, the amount of the catalyst contained in the liquid A is generally 0.2 to 10 parts by mass, preferably 0.4 to 8 parts by mass, based on 100 parts by mass of the polyol in the liquid A. More preferably, it is contained in a ratio of 1 to 6 parts by mass. If the content of the catalyst in the liquid A is less than 0.2 parts by mass, there is a problem that the contribution to the reaction is small and the strength development is delayed, while if it is more than 10 parts by mass, the reaction becomes too fast. Therefore, it becomes difficult to control the reaction rate.

In addition to the foaming agent and the catalyst described above, various additives similar to those used in the prior art may be added to the liquids A and B constituting the chemical liquid composition for polyurethane foam according to the present invention, depending on the purpose of use thereof. Is possible. Examples of such an additive include a defoaming agent and a thickening agent. These additives are used in a ratio of 0.1 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyol constituting the liquid A.

Specifically, the defoaming agent is used to uniformly arrange the cell structure of the foam formed by the reaction between the liquid A and the liquid B. Examples of the foam stabilizer include silicone, nonionic surfactant, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, and lauryl fatty acid ethylene oxide. Additives and the like are mentioned, and among these, silicone and nonionic surfactants are preferably used. These may be used alone or in combination of two or more. Further, among the defoaming agents, silicone-based defoaming agents are more preferable, and among them, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymer and the like are preferably used.

Further, the thickener is used as a solvent, is dissolved in the liquid A or the liquid B, and has a function of reducing the thickness of those liquids. Therefore, as long as it has such a function, it is not particularly limited, and for example, alcohols such as methanol and ethanol, ethers such as ethyl cellsolve and butyl cellsolve, and cyclic compounds such as γ-butyrolactone. Examples thereof include esters, dicarboxylic acid methyl esters, esters such as ethylene glycol monomethyl ether acetate, and petroleum hydrocarbons. These may be used alone or in combination of two or more.

Furthermore, in the present invention, flame retardants other than phosphoric acid esters can also be used. Examples of flame retardants other than phosphoric acid esters include red phosphorus, bromine-containing flame retardants, chlorine-containing flame retardants, phosphate-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, inorganic flame retardants, and metal hydroxides. You can list things. These can be used alone or in combination of two or more.

In the polyurethane foam chemical liquid composition comprising the liquid A containing a polyol as a main component and the liquid B containing a polyisocyanate as a main component containing the above-mentioned components, the liquid A and the liquid B are mixed in the field, and the mixture thereof. However, for example, in the injection backfilling method, the material is injected into a gap formed between the tunnel lining and the ground on the back surface, and is foamed and hardened there. By using the chemical composition of the present invention, for example, even when molded into a relatively thick wall, the generation of scorch is advantageously suppressed, the risk of self-ignition is remarkably low, and further, inside the foam. It is possible to obtain a polyurethane foam in which the generation of cracks is also advantageously suppressed.

Hereinafter, the present invention will be described in more detail by showing some examples of the present invention, but the present invention is not subject to any restrictions by the description of such examples. Needless to say. Further, in addition to the following examples, various changes and modifications to the present invention are made based on the knowledge of those skilled in the art, as long as they do not deviate from the gist of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.

Regarding the liquids A and B according to the following Examples and Comparative Examples, the evaluation of the flammability of the foam obtained by using them and the evaluation of the occurrence status of internal cracks and scorch are described, respectively. The procedure was as follows. In addition, both "%" and "part" shown below are based on mass.

-Evaluation of flammability-
From the obtained foam, five test pieces having a size of thickness: 13 mm × length: 150 mm × width: 50 mm were cut out, and the test pieces were used according to the test method B of JIS-A-9511. The combustibility test is performed and the measured burning time and burning distance are evaluated according to the following criteria. In addition, the evaluation of ○ or more is passed.
(1) Combustion time ⊚: The flame extinguishing time of all five test pieces is within 1 minute and 30 seconds.
◯: The flame extinguishing time of all five test pieces is within 2 minutes.
Δ: Although the extinguishing time of at least one of the test pieces exceeds 2 minutes, the average extinguishing time of the five test pieces is within 2 minutes.
X: The average flame extinguishing time of 5 test pieces exceeds 2 minutes.
(2) Combustion distance ⊚: The combustion distance of all five test pieces is 30 mm or less.
◯: The burning distance of all five test pieces is 60 mm or less.
Δ: Although the burning distance of at least one of the test pieces exceeds 60 mm, the average burning distance of the five test pieces is 60 mm or less.
X: The average burning distance of the five test pieces exceeds 60 mm.

-Evaluation of the occurrence of internal cracks-
Prepare a flexible container bag (flexible container bag) with a diameter of 1000 mm and a height of 1000 mm. Liquids A and B according to Examples and Comparative Examples are mixed at a ratio of liquid A: liquid B = 1: 2 (volume ratio), and the mixed liquid is injected into a flexible container bag to form a 1 m ³ foam. To make. The foam is left to stand in an environment of 25 ° C. for 24 hours, then cut in half in the vertical direction of the foam, and the presence or absence of cracks on the cut surface is visually observed by five panelists. After that, each panelist gives a score according to the following criteria, and the average value of the scores given by each panelist is calculated. If the average value is 3 points or more, it is considered as a pass.
4 points: No cracks are found.
3 points: Fine cracks that do not affect the physical characteristics are observed.
2 points: Small cracks are observed.
1 point: Many cracks are observed.

-Evaluation of the occurrence of scorch-
Prepare a flexible container bag (flexible container bag) with a diameter of 1000 mm and a height of 1000 mm. Liquids A and B according to Examples and Comparative Examples are mixed at a ratio of liquid A: liquid B = 1: 2 (volume ratio), and the mixed liquid is injected into a flexible container bag to form a 1 m ³ foam. To make. The foam is left to stand in an environment of 25 ° C. for 24 hours, then cut in half in the vertical direction of the foam, and the presence or absence of scorch on the cut surface is visually observed by five panelists. After that, each panelist gives a score according to the following criteria, and the average value of the scores given by each panelist is calculated. If the average value is 3 points or more, it is considered as a pass.
4 points: No scorch is allowed.
3 points: Slight discoloration is observed.
2 points: Discoloration is observed.
1 point: Remarkably discolored and burnt.

Chemical solution compositions for polyurethane foam (solutions A and B) containing each component at the ratios shown in Tables 1 to 5 below were prepared. In some examples, the content of the foaming agent is changed, but in order to evaluate the occurrence of internal cracks, the density of the foam (polyurethane foam) finally obtained is changed. It is necessary to make them substantially the same, and the content of the foaming agent is changed so that the density of the obtained foam is 27.5 to 32.5 kg / m ³ . The raw materials used in the preparation of solutions A and B are as follows.
-Polyol: Polyoxypropylene glycol
(Manufactured by Asahi Glass Co., Ltd., product name: EXCENOL 420, initiator: propylene glycol, alkylene oxide: propylene oxide 100% by mass, hydroxyl value: 280 mgKOH / g)
-Polyol: Glycerin-based polyether polyol
(Manufactured by Asahi Glass Co., Ltd., product name: EXCENOL 430, initiator: glycerin, alkylene oxide: propylene oxide 100% by mass, hydroxyl value: 400 mgKOH / g)
-Polyol: Ethylenediamine-based polyether polyol
(Manufactured by Asahi Glass Co., Ltd., product name: EXCENOL 500ED, initiator: ethylenediamine, alkylene oxide: propylene oxide 100% by mass, hydroxyl value: 500 mgKOH / g)
-Polyol: Mannich-based polyether polyol
(Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: DK polyol 3776, initiator: Mannich condensate, alkylene oxide: ethylene oxide and propylene oxide adduct, hydroxyl value: 350 mgKOH / g)
-Polyol: Ethylenediamine-based polyether polyol
(Manufactured by Asahi Glass Co., Ltd., product name: EXCENOL 750ED, initiator: ethylenediamine, alkylene oxide: propylene oxide 100% by mass, hydroxyl value: 750 mgKOH / g)
-Polyol: Bisphenol A-based polyether polyol
(Manufactured by Aoki Oil & Fat Industry Co., Ltd., Product name: Blaunon BEO-10AE, Initiator: Bisphenol A, alkylene oxide: Ethylene oxide 100% by mass, Hydroxyl value: 171 mgKOH / g)
-Polyisocyanate: Mangeka Kagaku Japan Co., Ltd., Product name: Wannate PM-200
・ Defoaming agent: Silicone-based defoaming agent
(Made by Momentive Performance Materials Japan GK, product name: NIAX Silicone L-6970)
-Flame retardant: Phosphate ester
(TMCPP manufactured by Daihachi Chemical Industry Co., Ltd .: Tris (1-chloro-2-propyl) phosphate)
-Flame retardant: Phosphate ester
(Made by Daihachi Chemical Industry Co., Ltd., TEP: Triethyl phosphate)
-Catalyst: Tertiary amine catalyst
(Made by Kao Corporation, Product Name: Kaorizer No.120)
・ Catalyst: Quaternary ammonium salt
(Made by Kao Corporation, Product Name: Kaorizer No. 420)
・ Catalyst: Potassium acetate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
・ Catalyst: Sodium acetate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
・ Foaming agent: HFC245fa
(Manufactured by Central Glass Co., Ltd., 1,1,1,3,3-pentafluoropropan)
-Effervescent agent: HFO-1336mzz
(Chemours, 1,1,1,4,4,4-hexafluoro-2-butene)
-Effervescent agent: HCFO-1233zd
(Honeywell, 1-chloro-3,3,3-trifluoropropene)

Liquids A and B according to each of the examples and comparative examples were uniformly mixed at a volume ratio of liquid A: liquid B = 1: 2 and foamed and cured to obtain a desired foam. .. After confirming that the density of the obtained foam is in the range of 27.5 to 32.5 kg / m ³ , the combustibility of the foam and the occurrence of internal cracks and scorch are according to the above-mentioned method. Was evaluated. The evaluation results are also shown in Tables 1 to 5 below.

As is clear from the results in Tables 1 to 5, in the polyurethane foam chemical solution composition according to the present invention (Examples 1 to 27), the foam obtained by using the chemical solution composition has internal cracks. It is confirmed that the generation of scorch is advantageously suppressed and the flame retardancy is also excellent. Further, by comparing Example 4 and Example 26, and by comparing Example 5 and Example 27, in the present invention, the carbonate compound (propylene carbonate) is contained in either solution A or solution B. However, it is recognized that it exerts an excellent effect.

Claims (10)

In a chemical liquid composition for polyurethane foam, which comprises a liquid A containing a polyol as a main component and a liquid B containing a polyisocyanate as a main component.
The polyol contains i) a polyether polyol having a hydroxyl value of 30 to 700 mgKOH / g in a proportion of 90% by mass or more, and ii) 95% by mass or more of the alkylene oxide added to the initiator. Contains a polyether polyol which is a propylene oxide in a proportion of 60% by mass or more.
One or more carbonate compounds selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, styrene carbonate, isobutylene carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl dicarbonate and diphenyl carbonate , and phosphoric acid. The ester is independently contained in at least one of the liquid A and the liquid B, respectively .
The carbonate compound is contained in a ratio of 0.3 to 12 parts by mass with respect to 100 parts by mass of the polyol.
A chemical composition for polyurethane foam. The chemical composition for polyurethane foam according to claim 1 , wherein the phosphoric acid ester is contained in a ratio of 20 to 70 parts by mass with respect to 100 parts by mass of the polyol. The chemical composition for polyurethane foam according to claim 1 or 2 , wherein the polyether polyol contains polypropylene glycol obtained by using any of propylene glycol, glycerin or bisphenol A as an initiator and adding propylene oxide to the initiator. thing. The chemical composition for polyurethane foam according to claim 3 , wherein the polyether polyol further contains polypropylene glycol obtained by using ethylenediamine as an initiator and adding propylene oxide to the initiator. The chemical composition for polyurethane foam according to any one of claims 1 to 4 , wherein the polyol contains a Mannig-based polyether polyol in a proportion of 10 to 40% by mass. The chemical composition for polyurethane foam according to any one of claims 1 to 5 , wherein the carbonate compound is propylene carbonate. The chemical solution composition for polyurethane foam according to any one of claims 1 to 6 , wherein the solution A contains a catalyst. The chemical composition for polyurethane foam according to claim 7 , wherein the catalyst contains a metal acetate. The chemical composition for polyurethane foam according to claim 8 , wherein the metal acetate is potassium acetate. The polyurethane according to any one of claims 1 to 9 , wherein water as a foaming agent is contained in the liquid A at a ratio of 1 to 10 parts by mass with respect to 100 parts by mass of the polyol. Foam chemical composition.